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Carbon Monoxide Rich Methanation Kinetics on Supported Rhodium and Nickel

Daniel Keehan, First LieutenantHQDA, MILPERCEN (DAPC-OPA-E)200 Stovall StreetAlexandria, VA 22332 D T IC

OCT 25 1988)

Final Report: 14 August 1988

Approved for public release; distribution unlimited

A thesis submitted to the University of Houston, Houston, TX 77004in partial fulfilment of the requirements for the degree of Masterof Science; Chemical Engineering.

IL)o

Dedicated to my wife Joan.

Acceslo-no

NTIS C R, 1 1

ji

CARBON MONOXIDE RICH METHANATION KINETICS ON SUPPORTED

RHODIUM AND NICKEL CATALYSTS

A Thesis

Presented to

The Faculty of the Department of Chemical Engineering

University of Houston

In Partial Fulfilment

of the Requirements for the Degree

Master of Science in Chemical Engineering

By

Daniel Keehan

August 1988

88 1024



By

Daniel Keehan

Approved:

Chemical Engineering

Committee Members: / (".' C" V 'l ." - -

D.J. Economou, Assistant ProfessorChemical Engineering

A.F Hildebrandt, ProfessorPhysics

Charles Dalton, Associate Dean D. Luss, Professor and ChairmanCullen College of Engineering Chemical Engineering

Acknowledgements

This research was supported by Sandia National Laboratories under contract No.

64-3924. Special thanks to Dr. J. D. Fish for his useful contributions and discussions.

The catalyst testing facility was constructed with a grant from the Energy Laboratory,

University of Houston and Texas Energy and Natural Resources Advisory Council.

I wish to express my appreciation and gratitude to my advisor, Dr. J. T.

Richardson, for his guidance and advice throughout the course of this work, and for his

help during the interpretation phase of this project.

I would also like to acknowledge the help and insight of Dr. Shirish Paripatyadar

during the experimentation phase of this study.

Many thanks to my fellow graduate students, Steve Stanley and Richard Shao, for

their helpful discussions.

I wish to express my thanks to Marvin Crawford, Michael Ward, David Dawlearn,

and John Lehman for fabrication and maintenance of equipment and electronics.

iv



An Abstract of a Thesis

Presented to

The Faculty of the Department of Chemical Engineering

University of Houston

In Partial Fulfillment

of the Requirements for the Degree

Master of Science in Chemical Engineering

By

Daniel Keehan

August 1988

Abstract

The utilization of CO2 reforming of methane in a solar based Chemical Energy

Transmission System (CETS) reliesgreatly upon the development of suitable catalysts for

both the endothermic and exothermic reactions. CO2 reforming of methane produces

hydrogen and carbon monoxide at a ratio of about one, thus requiring the methanation

reaction on the other side of the closed loop CETS to utilize this feed. H2/CO ratios lower

than three favor the formation of carbon with industrial methanation catalysts. Preliminary

tests performed on methanation with rhodium and nickel catalysts produced two, 0.5%

RhiA] 20 3 and 70% Ni/A120 3, for further study.

Kinetic experiments were conducted in an isothermal continuous stirred tank reactor

constructed of a copper alloy which prevented carbon formation on reactor parts. These

experiments were performed on pelleted 0.5% Rh/A120 3 in the 400 to 5000C range and

pelleted 70% Ni/A120 3 in the 300 to 500"C temperature range. In most experiments steam

was added to the reactor feed to inhibit carbon formation. Langmuir- Hinshelwood

expressions were fitted to experimental data for both catalysts and are suitable for reactor

design purposes.

Lifetime studies, at high CO conversion, were conducted with both catalysts.The

catalyst, 0.5% Rh/A1203, resists carbon formation very well and is recommended for

application at temperatures above 4000C. The nickel-containing catalyst, 70% Ni/A120 3,

has a high carbon formation resistance at temperatures below 350'C and is suitable for

application in the 300 to 350'C temperature range.

vi

Table of Contents

Chapter Page

I Introduction ................................................................ 1

1.1 Solar CETS1.2 Methanation1.3 Objectives

2 Experimental Equipment .................................................. 1 6

2.1 Reactor Design2.2 Gas Metering and Mixing2.3 Process Flow2.4 Gas Sampling2.5 Product Analysis2.6 Process Control

3 Experimental Procedure .............................................. 41

3.1 Equipment Calibration3.2 Reactor Testing3.3 CSTR Loading3.4 Catalyst Testing

4 Results and Discussion - 0.5% Rh .................................. 51

4.1 Review of Experimental Procedure4.2 Data Analysis4.3 Results Without Steam in the Feed4.4 Results With Steam in the Feed4.5 Kinetic Expressions4.6 Kinetic Expressions at High Conversion4.7 Lifetime Study

5 Results and Discussion - 70% Ni ................................... 94

5.1 Review of Experimental Procedure5.2 Data Analysis5.3 Experimental Results5.4 Kinetic Expressions5.5 Kinetic Expressions at High Conversions5.6 Lifetime Study

6 Conclusions and Recommendations ................................... 112

R eferen ce s .......................................................................... 114

A pp en d ices ......................................................................... 116

vii

List of Figures

Figure Page

1.1 Schematic CETS 2

1.2 Equilibrium Constants For Carbon Formation Reactions 5

1.3 Central Receiver System 7

1.4 Distributed Dish Receiver 7

1.5 ADAM Methanator Configuration 10

1.6 Carbon Deposition Boundaries 11

1.7 Solar CETS Methanator Configuration 13

2.1 Unmodified Autoclave Pressure Vessel 19

2.2 Autoclave Magnetic Drive System 20

2.3 Pressure Vessel Insert 21

2.4 CSTR Dead Volume Insert 23

2.5 CSTR Catalyst Basket 24

2.6 Impeller Shaft Sheath, Basket Bottom Plate 25Impeller, and Impeller Lock Nut

2.7 Assembled Reactor 26

2.8 Gas Metering and Mixing 28

2.9 Water Evaporating Column 29

2.10 Process Flow 31

2.11 Valco Ten-Port Valve 33

2.12 Process Control System Layout 37

4.1 Methanation Rate versus H2 Partial Pressure0.5% Rh, 400°C (No Steam in Feed) 55

4.2 Methanation Rate versus CO Partial Pressure0.5% Rh, 400'C (No Steam in Feed) 55

4.3 Methanation Rate versus H2 Partial Pressure0.5% Rh, 4501C (No Steam in Feed) 56

viii

4.4 Methanation Rate versus CO Partial Pressure0.5% Rh, 4500C (No Steam in Feed) 56

4.5 Methanation Rate versus H2 Partial Pressure0.5% Rh, 5000C (No Steam in Feed) 57

4.6 Methanation Rate versus CO Partial Pressure0.5% Rh, 500'C (No Steam in Feed) 57

4.7 Shift Rate versus H2 Partial Pressure0.5% Rh, 400'C (No Steam in Feed) 58

4.8 Shift Rate versus CO Partial Pressure0.5% Rh, 4000C (No Steam in Feed) 58

4.9 Shift Rate versus H2 Partial Pressure0.5% Rh, 450'C (No Steam in Feed) 59

4.10 Shift Rate versus CO Partial Pressure

0.5% Rh, 450'C (No Steam in Feed) 59

4.11 Shift Rate versus H2 Partial Pressure0.5% Rh, 500cC (No Steam in Feed) 60

4.12 Shift Rate versus CO Partial Pressure 0.5% Rh,500"C (No Steam in Feed) 60

4.13 Methanation Rate versus H2 Partial Pressure0.5% Rh, 400'C (Steam in Feed) 62

4.14 Methanation Rate versus CO Partial Pressure0.5% Rh, 400'C (Steam in Feed) 62

4.15 Methanation Rate versus H2 Partial Pressure0.5% Rh, 450C (Steam in Feed) 63

4.16 Methanation Rate versus CO Partial Pressure0.5% Rh, 4501C (Steam in Feed) 63

4.17 Methanation Rate versus H2 Partial Pressure0.5% Rh, 500C (Steam in Feed) 64

4.18 Methanation Rate versus CO Partial Pressure0.5% Rh, 500'C (Steam in Feed) 64

4.19 Shift Rate versus H2 Partial Pressure 0.5% Rh, 400'C (Steam in Feed) 65

ix

4.20 Shift Rate versus CO Partial Pressure 0.5% Rh, 400°C (Steam in Feed) 65

4.21 Shift Rate versus H2 Partial Pressure 0.5% Rh, 450 0C (Steam in Feed) 66

4.22 Shift Rate versus CO Partial Pressure 0.5% Rh, 450'C (Steam in Feed) 66

4.23 Shift Rate versus H2 Partial Pressure 0.5% Rh, 500'C (Steam in Feed) 67

4.24 Shift Rate versus CO Partial Pressure 0.5% Rh, 500'C (Steam in Feed) 67

4.25 Comparison of Methanation Rate versus H2 Partial Pressure 68With and Without Steam 0.5% Rh, 400'C

4.26 Comparison of Methanation Rate versus CO Partial Pressure 68With and Without Steam 0.5% Rh, 400'C









4.35 Comparison of Methanation Rate versus H2 Partial Pressure 73With and Without Steam 0.5% Rh, 500°C

4.36 Comparison of MeLhanation Rate versus CO Partial Pressure 73With and Without Steam 0.5% Rh, 500'C

x

4.37 Comparison of Methanation Rate versus H2 Partial Pressure 74With and Without Steam 0.5% Rh, 4000 C

4.38 Comparison of Methanation Rate versus CO Partial Pressure 74

With and Without Steam 0.5% Rh, 400'C


4.40 Comparison of Methanation Rate versus CO Partial Pressure 75With and Without Steam 0.5% Rh, 450 0C


4.42 Comparison of Methanation Rate versus CO Partial Pressure 76With and Without Steam 0.5% Rh, 5000C

4.43 Comparison of Shift Rate versus H2 Partial Pressure 78With and Without Steam 0.5% Rh, 4000C

4.44 Comparison of Shift Rate versus CO Partial Pressure 78With an(' Without Steam 0.5% Rh, 400'C

4.45 Comparison of Shift Rate versus H2 Partial Pressure 79With and Without Steam 0.5% Rh, 450°C

4.46 Comparison of Shift Rate versus CO Partial Pressure 79With and Without Steam 0.5% Rh, 450'C

4.47 Comparison of Shift Rate versus H2 Partial Pressure 80With and Without Steam 0.5% Rh, 500'C

4.48 Comparison of Shift Rate versus CO Partial Pressure 80With and Without Steam 0.5% Rh, 5000 C




xi

4.52 Comparison of Shift Rate versus CO Partial Pressure 82With and Without Steam 0.5% Rh, 450°C

4.53 Comparison of Shift Rate versus H2 Partial Pressure 83With and Without Steam 0.5% Rh, 500°C


4.55 Comparison of Shift Rate versus H2 Partial Pressure 84

With and Without Steam 0.5% Rh, 400'C

4.56 Comparison of Shift Rate versus CO Partial Pressure 84With and Without Steam 0.5% Rh, 400°C





4-61 Lifetime Study 0.5% Rh, 400'C 93

5.1 Methanation Rate versus H2 Partial Pressure (70% Ni,300°C) 98

5.2 Methanation Rate versus CO Partial Pressure (70% Ni,300°C) 98


5.4 Methanation Rate versus CO Partial Pressure (70% Ni,350'C) 99



5.7 Methanation Rate versus H2 Partial Pressure (70% Ni,500*C) 101


xii

5.9 Shift Rate versus H2 Partial Pressure (70% Ni,300 0C) 102

5.10 Shift Rate versus CO Partial Pressure (70% Ni,300 0C) 102

5.11 Shift Rate versus H2 Partial Pressure (70% Ni,3500 C) 103

5.12 Shift Rate versus CO Partial Pressure (70% Ni,3500 C) 103

5.13 Shift Rate versus H2 Partial Pressure (70% Ni,4000C) 104

5.14 Shift Rate versus CO Partial Pressure (70% Ni,400°C) 104

5.15 Shift Rate versus H2 Partial Pressure (70% Ni,500°C) 105

5.16 Shift Rate versus CO Partial Pressure (70% Ni,500'C) 105

5.17 Lifetime Study 70% Ni,300C 110

5.18 Lifetime Study 70% Ni,3500 C 110

5.19 Lifetime Study 70% Ni,400°C 110

xiii

List of Titbles

Table Page

1.1 CETS Reactions 3

1.2 Reactions Associated With Methanation 12

1.3 Properties of 0.5% Rh Catalyst 14

2.1 ADIO Card Addresses AOC Card: Slot 2 38

2.2 ADIO Card Addresses INT Card: Slot 7 38

2.3 ADIO Card Addresses AIM Card: Slot 0 39

2.4 ADIO Card Addresses DOT Card: Slot 5 40

3.1 Response Factors and Retention Times 43

3.2 Reactor Assembly / Disassembly Procedure 45

3.3 0.5% Rhodium Catalyst Experimental Runs Without Steam 47

3.4 0.5% Rhodium Catalyst Experimental Runs With Steam 48

3.5 70% Nickel Catalyst Experimental Runs 49

4.1 Surface Areas of 0.5% Rh Catalyst 54

4.2 Regression Coefficients 89

4.3 Comparison of Calculated Methanation Rate to ExperimentalResults for 0.5% Rh 89

4.4 Comparison of Calculated Shift Rate to Experimental Resultsfor 0.5% Rh 90

5.1 Comparison of Calculated Methanation Rate to ExperimentalResults for 70% Ni 107

5.2 Comparison of Calculated Shift Rate to Experimental Resultsfor 70% Ni 107

xiv

CHAPTER 1

INTRODUCTION

A Chemical Energy Transmission System (CETS) [1] is a process for storing

energy from a main energy source in the form of chemical binding energy through a

reversible endothermic reaction. This stored energy is transported through a pipe line to a

location where the energy is released, via the reverse exothermic reaction, for public or

industrial consumption (Figure 1.1). The energy to drive the endothermic storage reaction

comes from either fossil fuels, nuclear fuel, or the sun. Of these energy sources, the sun is

the least expensive and the cleanest. With the present fossil fuel situation, industry is

finding more direct applications for carbon based fuels as raw materials in specialty

chemical production, which makes them more valuable as a raw material than as a heat

generating fuel. Use of nuclear fuel as an energy source grows more difficult each day due

to increased cost of the fuel, difficulty and expense of disposing of process waste, and

rising public and governmental regulation of the industry. In West Germany a nuclear

based CETS, the EVA-ADAM [21,was constructed for experimental purposes. The

success of this experimental unit demonstrated that steady-state operation of a CETS is

possible. The work presented in this thesis was done in support of the design and

development of a solar based CETS by the Sandia National Laboratories, Albuquerque,

New Mexico.

1.1 Solar CETS

In order for any CETS to be successful, the right energy storage/release reaction

must be chosen. The primary criterion a reaction must meet is that it must be reversible and

have high conversions in the temperature range covered by the CETS. For a solar based

I

Chemical Energy Transmission System(CETS)

Xt'XG

T T -

Enaotherm: X ExothermicReaction Reaction

A+SA~B- XX +ZZ XY- A.+B

PIPELINE

Fossil Fuels Process Heat

Nucleor Reactor

Solar Tower

Figure 1. 1Schematic CETS I I]

2

CETS the endothermic reaction is carried out at between 800 and 1200C and the

exothermic reaction between 300 and 5500C. The reaction also must be catalyticaly

induced so the reaction can be controlled. Of the many reactions known, five were chosen

as the most promising [1] (Table 1.1). Additional conditions must be met: 1) the reaction

should have a high transmission capacity, i.e., energy transferred per gram of reactants, 2)

there must be no side reactions producing contaminants that accumulate in the closed loop,

3) the reaction must not generate or consume compounds which are toxic, corrosive, or

explosive, and 4) the reaction should be one which has been developed industrially, thus

avoiding extensive work on basic technology.

Table 1. 1

CETS Reactions [1]

Chemical Reaction kJ g-I

CH4 + H20 4* CO + 3H 2 6.06 {1. }CI-H +C02 4:* 2CO + 2H 2 4.12 {1.2}2NH 3 <-> N2 + 3H 2 3.86 {1.3}

C6H1 2 <-* C6H6 +3H 2 2.84 { 1.4}2SO 3 < 2SO 2 + 02 1.52 {1.5}

Of the reactions in Table 1.1, steam reforming of methane, {1.1}, is the most

promising [1]. Steam reforming of methane is an established process in the chemical

industry. Catalyst and reactor technology is advanced and has been proven. High

conversions have been obtained for the endothermic reforming reaction, and catalysts and

technology exist for methanation to produce a high temperature exothermic reaction [3,4].

The main problem with steam reforming is the formation of carbon on the catalyst. This

occurs by one of two reactions:

CH4 <- C + 2H 2 11.6}

3

2CO * C + C0 2 { 1.7}

The equilibrium constants for these reactions are shown in Figure 1.2, and are measured

for nickel catalysts [5]. Reaction { 1.6} is favored at high temperatures such as those

encountered in a methane reformer, whereas Reaction {1.7} is favored at lower

temperatures found in methanators. The problem of carbon formation in the reformer can

be solved by using two to three times the stoichiometric amount of steam in the feed to ahe

reformer [3,61. This removes the carbon by the reaction,

C + H20 : CO + H2 {1.8}

Carbon formation in the methanator can be halted by using excess hydrogen in the feed to

drive the reaction [3],

H2 + C 4- 4 CH { 1.9}

The next most promising reaction is CO 2 reforming of methane, {1.2}. This

reaction has a high transmission capacity and is reversible with high conversion over the

operating temperatures encountered in a solar based CETS. The main problem with CO2

reforming is that little commercial use has been made of this reaction, and there are no

proven catalysts and reactor technology. With present commercially available reforming

catalysts, severe coking occurs on the catalyst [7,8]. Without steam in the feed, Reaction

f1.6} is not countered by Reaction {1.8}. This leads to rapid deactivation of the

commercial nickel catalysts by coke formation. Excess CO2 can be added to the feed of the

reformer to suppress Reaction { 1.71, but the excess CO 2 in the product stream suppresses

the methanation reaction. Also CO 2 reforming of methane produces a product stream in

which the H2/CO ratio is about one. This low ratio causes severe coking on presently

available methanation catalysts [4]. Steam reforming and CO 2 reforming appear to be

similar processes thus some of the reactor technology developed for steam reforming could

be applied to CO 2 reforming. The principal obstacle left in the application of CO 2

reforming to a solar based CETS is the development of catalysts which resist carbon

formation under the reforming and methanation reactor conditions.

4

i2

2C0=C +C0 2

10

Kp CH4 = C + 2H 2

CO +H2= C + H20_

1

0 .1 1 1___ 1___ 1___ 1___ 1_ __ __

400 600 800 1000

TEMPERATURE, 0C

Figure 1.2Equilibrium Constants For Carbon Formation Reactions [5]

5

Ammonia synthesis (Reaction {1.31) is an exothermic reaction favored at high

pressures [9]. For high conversion the reactor must be operated at low temperature and

high pressure with recycle. Typical ammonia reactors operate at 200 to 300 bar and 400 to

500'C. The considerable amount of compression for reactor pressure and recycle tends to

discourage use of ammonia synthesis as an economical candidate for a chemical storage

reaction in a solar based CETS.

Hydrogenation of benzene (Reaction { 1.41) on an industrial scale is a very efficient

process [9]. Catalyst and reactor technology for this reaction have been proven. The main

concern about the use of this reaction is the toxicity of both benzene and cyclohexane.

These chemicals are handled commercially every day, but the danger involved in long

distance pipe line transmission makes this reaction unsuitable for the solar CETS.

Oxidation of sulfur dioxide (Reaction { 1.5}) was found to be a very promising

reaction [10]. The reaction is endothermic at atmospheric pressure and has no side

reactions. The reverse reaction has been chemically proven in the industrial production of

sulfuric acid. Difficulty with this reaction arises because of the corrosive nature of S03

whose interaction with various metals has not been thoroughly studied. These

metallurgical problems preclude the immediate use of the oxidation of sulfur dioxide in a

solar based CETS.

For solar CETS there are two types of receivers being considered. There is the

central receiver system (Figure 1.3) and the distributed receiver system (Figure 1.4). With

both, the use of steam reforming causes difficulty, since two to three times the

stoichiometric amount of steam must be added to the reformer feed to suppress carbon

formation on the catalyst. In both cases this steam must be generated on site, which is

possible via solar energy, but all the steam in the product stream must also be condensed

before the process gases can be transported at ambient conditions to the methanator. Some

of the steam could be used to operate the reforming facility, but much would be wasted.

With the distributed receiver system, the additional problem of insulating or heating the

6

.m ... ..... .

Central ReceiverTower

Solar rays

H eliostats

Figure 1.3Central Receiver System [I11

Reforne. Reactor

From MethanatorT

To Methanator

Figure 1.4

Distributed Dish Receiver

7

interconnecting lines to prevent condensation of the steam arises. This increases both

capital investment and operation cost.

An obvious solution is to eliminate steam in the reformer. This could be

accomplished with CO2 reforming of methane { 1.21. However, use of CO2 reforming

requires extensive research on the development of suitable catalysts and on the kinetics of

the CO 2 reforming reaction. Much of this work has been undertaken by Richardson and

coworkers at the University of Houston [7].

1.2 Methanation

Equally important is the question of the methanation side of the solar based CETS.

Methanation is a technically proven industrial process [4]. Today there are three main

applications: 1) elimination of CO from fuel gases to produce methane rich, high Btu value

fuels, 2) elimination of CO from feed gases in such processes as ammonia synthesis to

prevent catalyst poisoning, 3) production of Synthetic Natural Gas (SNG) from naphtha or

coal. Over the past 80 years, many studies have been conducted on catalytic methanation.

Summaries of this work are found in [4,11.12,13).

The nuclear based CETS, the EVA-ADAM, utilized steam reforming of methane in

EVA to store nuclear generated thermal energy, and methanation in ADAM to release the

stored chemical energy [1]. The EVA-ADAM and the second generation unit, EVAII-

ADAMII, were not designed to be highly efficient but rather to be flexible so that many

studies could be conducted on the one unit. Since the goal was research and not efficiency,

use of steam reforming and excess steam in the process was not of as great a concern as it

would be in a solar based CETS. EVA-ADAM demonstrated that a CETS can be operated

successfully, but for a solar-based CETS more care must be placed in the over-all process

design.

8

The methanator, ADAM, consisted of three adiabatic methanation reactors packed

with a nickel catalyst, each followed by heat exchangers (Figure 1.5). Due to the highly

exothermic nature of the methanation reaction, the feed stream to the first methanator was

diluted and the reaction carried out in three stages to prevent sintering of the nickel catalyst.

The first methanator was operated at an exit temperature of 6000 C,. and the last at about

300'C. No problems were reported with the nickel catalysts. Carbon formation was not

expected since steam reforming produces H2 and CO in a ratio higher than 3:1. For a solar

CETS using CO2 reforming, the methanation catalyst must resist coking at H2/CO ratios of

about 3ne, for successful methanator operation.

Methanation is a highly exothermic reaction. Table 1.2 shows the other reactions

which accompany Reaction {1.10}. As pointed out by Mills et al. [4], the hydrogenation

of CO2 { 1.11 1 does not occur when CO is present, thus Reaction { 1.11 } can be eliminated

from the competing reactions in the methanator since there will always be CO present. It

should also be noted that the water-gas shift reaction { I 12) is not strongly exothermic and

does not compete as strongly with Reaction { 1.10} for CO. The reaction which competes

the most and causes the most problem is the Boudouard reaction { 1.7}. This reaction is

one of the main causes of methanation catalyst failure and has been the topic of study for

many researchers [3,4,6].

As mentioned earlier, the deposition of carbon on the catalyst can be reduced or

eliminated by having a H2/CO ratio greater than three. Operation of many commercially

available methanation catalysts below a H2/CO ratio of three results in carbon formation

(Figure 1.6) [4,6], Since no catalyst exist for such low ratios and it is not feasible to inject

H2 into the closed-loop CETS, the only alternative is to develop a catalyst which does not

produ ,, carbon at H2/CO ratios of about one. Such ratios will be encountered in the

methanator of the CO2 reforming solar-based CETS.

9

300 C

Ni

650 C

300 C

Ni

475 C

300 C

Ni

325 C

Figure 1.5ADAM Methanator Configuration

I0

CA0160% DEPOS!O, MAY C.U'P N APEA SENEAT1 CLTF E

ty- 60C 700 goo 9y- 1,0cC' 1,10c I20 130TMRUO,'K.

Figure 1.6Carbon Depos ition Bou ndari es [ 11]

Table 1.2

Reactions Associated With Methanation [41

Chemical Reaction AHr4OOc (kcal toolI1)

3H 2 + CO * CH4 + H 20 -50.36 {1.10}4H 2 + CO2 < CH4 + 2H 20 -40.65 {1.J1}

CO + H20 CO2 + H2 -9.71 {1.12}

2CO 4-* C + CO 2 -41.43 {1.7}

The problem of carbon formation on the methanation catalyst at low H2/CO ratios

was addressed by Richardson and Cullinane [14]. Using a rapid catalyst screening method

[15], a 0.5% rhodium on alumina catalyst was discovered which catalyzed the methanation

reaction, had a low activation energy, and did not promote the formation of carbon at

H2/CO ratios as low as one. The properties of this catalyst can be seen in Table 1.3. This

catalyst performed very well over a range of operation conditions, but was found to be very

sensitive to impurities in the feed stream. such as iron carbonyl.When contacted with the

catalyst surface, the iron carbonyl decomposed and deposited iron which in turn catalyzed

the carbon formation reaction. The catalyst was also sensitive to iron impurities in the

alumina support. For successful use of this catalyst care must taken to eliminate all sources

of contamination.

The methanator design being considered for the CO2 reforming solar-based CETS

is similar to that used in the EVA-ADAM [1], except the last methanator is operated

isothermally instead of adiabatically (Figure 1.7). The reactants to the first two

methanators enter at a temperature of about 350"C and exit at about 500'C. The third

methanator is operated isothermally at about 300'C. At low temperatures the 0.5% Rh

catalyst was found to have low activity, in fact so low that the amount of catalyst required

to fill the third methanator was excessive. For this reason another catalyst with high

12

330 C

Rh

500 C

350 C

Rh

500 c

Ni 300 C

Figure 1.7Solar GETS Methanator Configuration

13

activity was necessary for the third methanator. This catalyst must have a high activity at

300C, and resist carbon formation under the methanator reactor conditions. Nickel

seemed to be the best choice because of its high activity and low cost, but the right catalyst

formula had to be found. The screening study [141 indicated that a proprietary methanation

catalyst, used for the production of SNG from naphtha and coal gasification, was suitable

at temperatures below 400*C. The catalyst contained 70% Ni and greater than 1% K on an

alumina support. The catalyst was known to resist carbon formation in conventional SNG

processes, but had to be tested under the reaction conditions that would be encountered in

the methanator.

Table 1.3

Properties of 0.5% Rh Catalyst [161

Commercial Nomenclature Engelhard 3253702, 0.5% Rhon 1/8" Alumina Pellets

Measured Rhodium wt.% 0.488Support Surface Area, m2g-1 90Pellet Density, g cm -3 1.75Bulk Density, g cm-3 1.04Pore Volume, cm 3g- 1 0.35Mean Mesopore Radius, A 30Mean Macropore Radius, A 3000Rhodium Surface Area, m2g-1 (Rh) 188Approximate "egg-shell" Thickness, cm 0.01

14

1.3 Objectives

Screening tests indicated the suitability of rhodium and nickel catalysts for high and

low temperature applications respectively. This thesis describes the determination of

kinetic expressions for the rate of methanation on both the 0.5% Rh and 70% Ni catalysts

in their pelleted state, and testing for extended periods of time at actual operating conditions

to determine their durability and suitability for this application.

15

CHAPTER 2

EXPERLMENTAL EQUIPMENT

The purpose of the research conducted during this study was to determine the rate

equations for the methanation reaction catalyzed by both 0.5% Rh and 70% Ni catalysts.

Much of the experimental equipment used was constructed and assembled by former

workers. The basic design of the reactor was that of Hadjigeorghjiou [17]. Torres-Acosta

[18] designed, constructed, and tested the catalyst testing unit which was later modified by

Cullinane [15]. This chapter describes the equipment used and notes any changes made.

For a more detailed description of the existing equipment, the three original sources should

be referenced.

The description of the experimental equipment is divided into the following

sections: Reactor design, gas metering and mixing, process flow, gas sampling, product

analysis, and process control.

2.1 Reactor Design

In choosing the type of catalytic reactor several factors were considered. These

were economics, catalyst form, ability to operate isothermally, ease of data analysis,

reactions being studied, and ability to operate at both very low and high conversion. A

preliminary screening of possible reactor types was conducted with the aid of the work of

Doraiswamy and Tajbl [19]. A Continuous Stirred Tank Reactor (CSTR), a Packed Bed

Reactor (PBR) without recycle, and a PBR with a recycle stream were considered.

The CSTR can be manufactured at moderate cost and designed to contain the 1/8"

catalyst pellets used in both the rhodium and nickel studies. It could also be constructed of

16

a metal which was inert to the methanation reaction being studied, and to side reactions. A

CSTR is also easy to control, and can be operated isothermally at both low and high

conversion. Data produced by the CSTR is easy to analyze because the CSTR is assumed

to be perfectly mixed, thus the concentration at the outlet is the concentration throughout the

reactor. This feature allows the data to be used without further manipulation.

The PBR without recycle may also be manufactured at a low cost and can be

operated at both low and high conversion, but its ability to operate isothermally depends on

the size of the catalyst bed [19]. Data obtained from the reactor must be statistically

analyzed to account for the differential conversion which occurs at each point along the

bed, together with the temperature change which may also be present in highly exothermic

reaction.

The PBR with recycle avoids some of these difficulties [19]. It may be operated

differentially by recycling a large portion of the effluent stream. This requires a positive

displacement pump to force the effluent gases across any pressure drop which develops in

the reactor. Reducing the recycle rate allows for operation at high conversion. Isothermal

operation may be possible depending upon the size of the catalyst bed and the rate of

reaction. When operated in the differential mode, the data give the reaction rates directly,

but when operated at a high conversion the data require extensive statistical analysis.

Of the reactors considered, the CSTR proved to be the best for this study. The

simple PBR without recycle was unsuitable for the following reasons. First, isothermal

operation can not be assured, which is essential for kinetic studies. Secondly, the data

must be statistically analyzed before a reaction rate can be determined. This involves

assumptions which lead to greater errors in the final rate expression. The PBR with recycle

has the disadvantage that a positive di ,placement metering pump must be specially

manufactured to be catalytically inert and operate at temperatures ranging from 300 to

500'C. The manufacture of such a pump is very costly. Also, at high conversion the data

still needs statistical analysis. The choice of a CSTR design was simplified by the

17

existence of a reactor which had been designed, built, and tested by Hadjigeorghiou [ 17] to

study high pressure methanation. The same reactor was used for these experiments after

some modifications.

The original reactor was a modified 300 cm 3 Autoclave stirred pressure vessel

(Figure 2.1). It was constructed of 316 stainless steel which is strong and durable, yet

catalyzes the coking reaction when the hydrogen to carbon monoxide ratio falls below

three. Coke deposition results mainly from the high nickel content of the steel [11]. This

fact was critical because the methanation reaction must be studied at H2/CO ratios between

one and two.

Therefore, the reactor was constructed of a metal having the smallest catalytic effect

in the presence of the gases produced and consumed by the reactions involved. Of the

metals investigated, copper proved to be the cheapest and most catalytically inert [4]. It

could also be used in the temperature and pressure ranges studied.

Initially, all parts of the reactor were to be copper plated, but it was found that

copper plating is easily damaged and may even peel after several heating and cooling

cycles. The next alternative was to make the reactor from pure copper. This was not

feasible because pure copper is not easily machined. The final alternative was to choose a

copper alloy which could be machined and yet does not contain any metals acting as

catalysts. Aluminum, Silicon, Bronze (CDA# 642: 91% Cu, 7% Si, 2% Al ) was chosen

as a suitable alternative. Aluminum, Silicon, Bronze (ASB) had all of the desired

characteristics required except it lacked the strength of 316 stainless steel. Since the

original Autoclave magnetic drive system (Figure 2.2) was used, the reactor itself remained

316 stainless steel. A design compromise was to use the 316 stainless steel pressure vessel

fitted with an ASB sheath, and to construct all of the internal parts of ASB.

18

MA%' PEASSEM9.1

PArET -2 W.

FIXE: VITY

Ij

CA,.

Figre2.Unmodified ~ ~ ~ OTO AuolaePrsur ese 10

1914:c

MAGNEDRIVE ASSEMBLY WITH ENCAPSULATED DRIVEN MAGNETS

ADAPTER-316 SS

0 -RING-TEFLON

Apo BEARING-CARBON GRAPHITE

TACHOMETER COIL

RETAINER-C STI.

-BEARING-CARBON GRAPHITEI __ ____ ____ ___ENCAPSULATED DRIVEN MAGNET ASSEMBLY

MOLDER-C STL

HOUSING- 316 SS

____OUTER MAGNET-INDOX V

SPACER-VINYL (not Shown)

RETAINER-C STL

ti SPACEP-C ST,

BEARING-COMM L

SNAP RING-STL

BEARING-CARBON GRAPHITE

SPACER-316 SS

GLANC-416 SS

COLL.AR-4:6 SSBEARiNG-CAPBON GRAPHITEGASKET-3IS SS

DRIVE SHAFT COMPLETE-316 SS

Figure 2.2Autoclave Magnetic Drive System [20]

20

This solution gives mechanical strength of the 316 stainless steel yet provides a reaction

environment which is catalytically inert.

Several improvements were made to the original design. First, the impeller blades

were made one eighth of an inch longer. This helped improve mixing. Secondly, the ends

of the basket were sealed by placing a plate on the bottom and sealing the top against the

dead volume insert. This eliminated any short circuiting and achieved a better perfectly

mixed state. Thirdly, flow channels were machined into both the upper and lower wire

supports, thus increasing gas circulation and providing gas exits at locations far from the

inlet tube. Finally, dual element, ungrounded Omega thermocouples were used to measure

bed and gas temperatures. This allowed the use of one probe to obtain measurements for

both the process control computer and the digital read-out box from the same location in the

reactor. Schematics of reactor parts appear in Figures 2.3 to 2.7.

A Research Incorporated Model 63911 Temperature Controller maintained the

desired temperature within the reactor. Initially the controller was connected to a

thermocouple in the reactor bed, since this gives the best results, but it lead to large

oscillations about the reactor setpoint. The oscillations were due to the lag time created by

the thick walls of the pressure vessel, which slowed heat transfer. To correct this the

controller was connected to a thermocouple in the reactor heating block, and gave the

required temperature within one degree Celsius.

2.2 Gas Metering and Mixing

The gas metering and mixing system was comprised of eight Tylan Model FC260

Mass Flow Controllers (MFC), Eight Tomco Solenoid Shut Off Valves (SSOV), seven

check valves, two Tylan Model RO 20A readout boxes, one Sage Instruments Model 220

21

= 22

00

go 113'16-4 149 '64--O- 34-

Figure 2.3Pressure Vessel Insert

22

4507

3/8, 8"-5 32"

C.,N NOTES

A) Threaded for 1.72 screws

B) Locate 7/64" from edge

C) Locate 6,116" from edge

0 -0 0 - r1 11/16"- l1 23,, 2"-- -"

7,Z78"

2 1 2

C 450

Figure 2.4CSTR Dead Volume Insert

23

5/32"

0@

-V

0 -0

8 0 co

00

1 23132- /

1 11/16"

0 0

TT

Figure 2.5CSTR Catalyst Basket

24

[ii 5 1 /4"

° --- 40- 4-1/32"

5 /8

,.-

5 16" NFT

/1 ' 313 2"

Figure 2.6Impeller Shaft Sheath, Basket Bottom Plate

Impeller, and Impeller Lock Nut

25

Figure 2.7

Assembled Reactor

26

Syringe Pump, two gas mixing chambers, and an iron carbonyl removal trap. A schematic

of tlhe system can be seen in Figure 2.8.

All gasses except water are metered by the MFCs. The Tylan controllers provide a

very accurate measurement and control of the gases. The controller consists of a control

valve, thermal sensors and the electronic circuitry required for the signals from an outside

readout box. The controllers operate on the principal of temperature change as a gas flows

through the meter. This temperature change is measured by two sensors, one at the inlet

and the other at the outlet. The measured temperature difference is transformed into an

electrical output signal which ranges from 0 to 5 volts dc. The circuitry of the meter creates

a linear signal over the range of flow for a particular gas. In this case the range is from 0 to

200 standard cubic centimeters per minute (sccm). Each MFC can be used for any gas or

mixture of gases by consulting the table of conversion factors provided in the Mass Flow

Instructions Manual [211. For these studies the MFCs were calibrated using a bubble

meter. The calibration curves can be seen in Appendix A. 1.

Water, in the form of steam, was injected into the system using a Sage Instruments

Model 220 Syringe Pump and a water evaporating column (Figure 2.9). The water

evaporating column was operated at 105'C and 1 atmosphere. The injection rate of water

(at 27°C, I atm) needed to produce a specified amount of steam at standard conditions

(0°C, 1 atm) was calculatied from the calibration curve shown in Appendix A.2.

After metering, the gases passed through check valves and Solenoid Shut Off

Valves (SSOV). The check valves were placed after the MFCs to protect them from

damage due to back flow in the system. The SSOVs were placed to allow computer control

of the gas flow through the data output card (DOT), and to stop all gas flow in the event on

an electrical outage.

Carbon monoxide, methane, carbon dioxide, and nitrogen were mixed and then

passed through a heated chamber containing 5 Angstrom pore size molecular sieve

adsorbent, to remove any traces of iron carbonyl present in the carbon monoxide feed gas.

27

H20 H2 CID OH 4 C02 N2

Supply Tanks

Mass FlowControllersSolenoid ShutOtt Valves

Syringe Check ValvesMeteringPump

Evaporator Manifold

Block

Mixer

iron CarbonylRemoval Trap

Mixer

Figure 2.8Gas Metering and Mixing

28

H2

1/8' 316 StainlessH20---O-Steel Spheres

1/4" 316 StainlessSteel Tubing

4-Furnace

1/16* Thermocouple

4 1/4" SwagelokUnion Tee

Figure 2.9Water Evaporating Column

29

Iron carbonyl forms from a reaction of carbon monoxide with iron at high pressure, such

as encountered in pressurized gas cylinders. As discovered in the early stages of this

research, iron carbonyl leads to deactivation of methanation catalysts. To remove the iron

carbonyl from the feed gas, two measures were taken. First, aluminum cylinders were

used to supply carbon monoxide. This reduced effectively the amount of iron carbonyl

present in the feed but did not eliminate a small amount produced in bulk storage.

Secondly, the molecular sieve trap was installed. As pointed out by Schay et al. [22], iron

carbonyl is decomposed on Cab-O-Sil and other adsorbents at about 125°C. The trap

proved to be successful. Magnetic analysis of the molecular sieve adsorbent showed that

iron was deposited on the surfaces [23].

Hydrogen was passed through the evaporating column to acqire a desired vapor

pressure of steam. Steam and hydrogen then joined the other reactant gases in a second

mixer, followed by a stream splitter. One branch flowed to a preheater followed by the

reactor, while the other passed to the chromatograph for analysis of the feed composition.

All tubing after the water evaporating column and after the iron carbonyl trap were

made of copper and were heated with electrical heating tapes. Copper was used to prevent

coke formation on the tube walls. The heaing tapes prevented steam from condensing.

2.3 Process Flow

The process flow diagram is shown in Figure 2.10. The original three reactor

system, designed by Torres-Acosta[18],was replaced with a single CSTR. Existing reactor

furnaces were modified to serve different functions. One was used for the water

evaporation column, the other for a preheater. MFCs, SSOVs, and check valves

previously used for controlling reactor feed flow were allocated different duties, two on the

hydrogen and nitrogen feed lines to increase the maximum system flow from 200 sccm to

30

From Metering & Mixing

Solenoid Shut0 Preheater Off Valve

CondenserCTR

Mass Flow

Controller

e ondenser Condenser

Sampling Valve

Sigma 115

Vent

Figure 2.10Process Flow

31

400 sccm, and the third on the feed sample line to give an accurate measurement of the feed

sample rate. This replaced the needle valve previously used.

Upon leaving the second mixer, the gas stream was split. One stream went to the

gas chromatogragh (GC) for analysis, while the other went to the reactor. The feed gas

sample stream passed through a check valve and a condenser before reaching the MFC. It

was important to remove all water before the gas passed through the MFC and the GC.

Condensing water tends to plug the MFC sensor ports, change the size of the feed

sampling loop, and disrupt the accurate analysis of the feed gas by the Thermal

Conductivity Detector (TCD) of the GC. The sample then passed through a SSOV to the

MFC so that the exact amount of gas leaving the system was known. This increased the

accuracy of the material balances performed on the system.

The reactor feed stream passed through a preheater consisting of a copper tube

packed with alumina. The gas, now at reaction temperature, next passed to the CSTR.

The product stream was carried by copper tubing to the condenser, where all of the water

was removed before analysis of the product stream by the GC. Here again, the water must

be removed to insure accurate analysis of the product stream. Analysis of the water content

of either the feed or product stream is not critical. Since the exact feed concentration is

known, a carbon balance allows for the calculation of the amount of water in the product

stream. This is explained in Chapter 4.

2.4 Gas Sampling

On-line gas sampling was accomplished with one Valco Ten-Port Valve [24], fitted

with an air actuator (Figure 2.11). The complex sampling system used by Torres-Acosta

[181 was no longer needed because there was only one reactor product stream, one feed

32

LOOPo Te-PrtVav

33E

sample stream, and one GC. This allowed the feed and product streams to be sampled

alternately.

2.5 Product Analysis

On-line feed and product analysis was conducted by a Perkin Elmer Sigma 1B

Analyzer equipped with a thermal conductivity detector (TCD). The sigma lB Analyzer

was interfaced with a Sigma 115 Console with Level 2 communications 125].

The Sigma 115 console is the key to the exact analysis of the feed and product

samples. The console receives the voltage signals from the TCD of the Sigma IB,

translates them to component peak areas, manipulates the data using a prescribed method,

and prints a report. The console has the ability to receive signals from two analyzers

simultaneously, control the physical conditions within each analyzer independently, analyze

data, and print reports for each analyzer.

The console uses a generated method [26] which controls physical conditins

within each analyzer, collects data over prescribed times, and analyzes data using different

analytical techniques specified by the user. The method used for the entire project is listed

in Appendix B. The response factors listed were obtained using the calibration routine

outlined in the Perkin Elmer Sigma 115 User Manual 127].

The sigma lB analyzer was equipped with two matched Supleco, 15 foot,

Carboseive B columns. The columns were designed to give good separation of low

molecular _~g,,ht molecules.

A 9% hydrogen in helium carrier gas was used in the study. This mixture was

recommended by Purcell and Ettre [28] to obtain a more linear, and thus more accurate,

analysis of hydrogen. Such a carrier mixture was not used by either Torres-Acosta 118] or

Cullinane [151.

34

The TCD of the Sigma 1B measures the concentrations of gases in a mixture by

comparing the thermal conductivity of the sample mixture, with the ther-nal conductivity of

the pure carrier. As the gas sample is carried through the Carboseive B GC columns, the

individual components of the mixture are adsorbed on the Carboseive B and released

individually at a certain rate, which is dependent upon the temperature of the columns.

This causes the individual components to elute at different times, thus the TCD can detect

the amount of a certain component by comparison with the pure carrier gas. Components

with a thermal conductivity higher than that of the carrier give a positive signal, those with

a lower thermal conductivity a negative signal.

The thermal conductivity of hydrogen is slightly smaller than that of helium because

hydrogen has a lower molecular weight. Similarly, components with a higher molecular

weight than helium produce a positive signal. As pointed out by Purcell and Ettre [28], if

the amount of hydrogen in the sample is below 8%, a positive signal results that is very

nonlinear with hydrogen concentration. If the amount of hydrogen in the sample is above

8%, a negative signal results which is linear with hydrogen concentration. Thus using 9%

hydrogen in the helium carrier gas gives a negative linear signal for hydrogen. The

negative signal was inverted and treated as a positive signal in the analysis of the sample

composition.

2.6 Process Control

In this section a brief description of the process control system is given, but for a

more detailed description the work of Torres-Acosta [181 and Cullinane [15] should be

consulted.

The heart of the process control system (Figure 2.12) is an Analog Devices

MACSYM 2 (Measurement and control System) process control computer. The MACSYM

35

2 uses a form of the Basic Programming Language called MACBASIC. MACBASIC

allows the use of English language type commands to creav control algorithms. Through

the use of MACBASIC, the MACSYM 2 was capable of real time operation and

multitasking [29].

Through a series of ADIO (Analog/DigitallInput/Output) cards, the MACSYM 2 is

able to communicate with the rest of the system. These cards are the analog to digital and

digital to analog interfaces needed for various control and data acquisition tasks.

There are several ADIO cards in service in the MACSYM 2. The interrupt card

(INT01) senses when the Sigma lB analyzer is ready for a sample to be injected. The

analog output card (AOC04) provides an analog signal to the temperature controllers. The

analog input card (AIMO3) reads the temperatures at various locations in the system. The

digital output card (DOT) produces an electrical signal which activates a bank of relays

which in turn activate the SSOVs. Tables 2.1 to 2.4 give the configuration of these cards.

The process control program used for these experiments is listed in Appendix E. I.

36

Computer SolenoidDOT CAR Shut-off Valves

.... CA Dj Mass FlowAOC CARD, Controllers

AIM CARDAOC CARD--.. 0" Temperature

ACCR0 Controllers

Computer Mode Manual LoopLoop Thermocouples

AIM CARD IDOT CARD - Sampling Valves

RS-232C LAnalysis (GasChromatograph)

RS-232C IINT CARD

Figure 2.12Process Control System Layout 118]

37

Table 2.1

ADIO Card AddressesAOC Card: Slot 2

Channel Controller

0 Iron Carbonyl TrapI Water Evaporator Column2 Preheater3 Reactor

Table 2.2

ADIO Card AddressesINT Card: Slot 7

Channel Event

0 GC 1 Ready Light1 Unused

7 Unused

38

Table 2.3

ADIO Card AddressesAIM Card: Slot 0

Channel Thermocouple

0 UnusedI Reactor: Inlet2 Unused3 Unused4 Water Evaporating Column5 Iron Carbonyl Trap6 Reactor: Catalyst Bed7 Unused8 Preheater9 Unused10 Unused11 Unused12 Reactor: Gas13 Unused14 Unused15 Unused

39

Table 2.4

ADIO Card Addresses

DOT Card: Slot 5

Channel Valve

0 N2I C022 CO3 CH44 H25 H2 Aux.6 N2 Aux.7 Feed Sample8 Unused9 Unused10 UnusedI1I Unused12 Injection Position A13 Injection Position B14 Unused15 Unused

40

CHAPTER 3

EXPERIMENTAL PROCEDURE

This section describes the experimental procedure used throughout the study.

Covered in this chapter are the procedures used for calibration of the equipment, testing of

the reactor, loading of the reactor, and measurements on the two catalysts studied.

3.1 Equipment Calibration

Proper calibration of the instruments was important to the accuracy and

reproducibility of the experimental results. Because of this fact the calibration of the

instruments was checked at the beginning of each series of experimental runs,

approximately every three months.

The calibration of the mass flow controllers (IFC) was done with a bubble meter at

the exit side of the MFC. The digital read-out was varied over the range of the meter (0 to

200 sccm) and the flow rates measured with the bubble meter. Measured flow rates were

then converted to standard conditions (0°C, I atm). The assumption of an ideal gas was

reasonable because the gases were at atmospheric pressure and 23°C. The ideal gas law

gave a correction factor of 0.92 to convert the measured volumetric flow rate in cubic

centimeters per minute to standard cubic centimeters per minute (sccm). Calibration curves

were then plotted comparing digital read-out and flow in sccm (Appendix A. 1). These

calibration curves eliminated the need for mechanical adjustments to the MFCs, as done by

Torres-Acosta [18], thus making the calibration procedure faster and more reliable.

The syringe pump was calibrated in a similar manner. The digital read-out was

varied over the range of the pump (0 to 1000) and deionized water collected over a thirty

minute period for each setting. The water was then weighed and the volumetric flow rate

41

determined. From the operation conditions of the water evaporation column (105C, 1

atm), the rate of steam production in sccm could be determined. The calculations and

calibration curve are shown in Appendix A.2.

Calibration of the Sigma 115 Gas Chromatograph (GC) was done following the

general instructions given in the Sigma 115 Console Instructions manual [26]. Before

calibration, the Carboseive B columns of the Sigma 1B analyzer were conditioned by

heating them to 195°C for eight hours while passing carrier gas through them. The

columns were then cooled to the operating temperature with the carrier gas flowing. After

conditioning the columns, an optimized operating temperature for the analyzer oven was

then determined. The temperature must be high enough to allow the sample to pass quickly

through the GC columns, yet low enough for a good separation of individual component

peaks. An optimum temperature was found by using an equimolar mixture of the gases as

a sample, and adjusting the temperature so that all peaks could be read distinctly. The

relative retention times of the various components were then determined by choosing one

component (carbon monoxide) as a reference.

In order for the Sigma 115 Console to compute the concentrations of the

components of the gas mixture, relative response factors must be determined. First, equal

volume samples of the pure gases were analyzed by the GC and their peak areas

determined. Secondly, all of the peak areas were divided by the peak area of the standard,

carbon monoxide, to yield the relative response factors (Table 3. 1).

The response factors and relative retention times were used to generate the operating

method (Appendix B). The response factors were then tested by analyzing gas samples of

known composition, thus fine tuning the factors to give more accurate results in the

concentration ranges being studied. Response factors used during this study differ from

those used by Torres-Acosta [18] and Cullinane [15] because of the different carrier gas.

42

Table 3.1

Response Factors and Retention TimesFor Sigma I B Analyzer

Component Retention Time Response Factor(Minutes)

Hydrogen 1.50 32.00Nitrogen 2.68 0.498Carbon monoxide 3.15 0.500Methane 5.80 0.595Carbon dioxide 12.5 0.426

The response factors of the GC method were recalculated each time a new cylinder

of carrier gas was installed. This was done because the composition of the hydrogen I

helium mixture changed slightly with each cylinder. Other than the response factors, all

other parameters remained the same throughout the study.

3.2 Reactor Testing

Before the reactor could be used with confidence, it was necessary to determine

whether it was a true CSTR and if the metal was catalytically inert. The reactor was

thoroughly cleaned with acetone to remove an), oils or other foreign materials left during

construction. It was assembled and heated to 500'C in the presence of nitrogen for twenty-

four hours to vaporize any residual oils or other contaminants, then cooled to room

temperature in nitrogen.

To determine whether the reactor was catalytically inert, it was loaded with 1/8"

alumina pellets and operated in the temperature range of 300 to 500'C with an equimolar

feed of carbon monoxide, carbon dioxide, methane, nitrogen, and hydrogen. Analysis

43

showed the same composition for feed and product streams, thus proving that the reactor

metal and the alumina pellets are catalytically inert.

The reactor design had been thoroughly tested by Hadjigeorghiou [17] who found it

to be a true CSTR. To confirm this the following mixing test was performed. After

loading the reactor with a full charge of catalyst (225 pellets), the temperature was

increased to 400'C, the catalyst reduced for four hours in hydrogen, and the feed mixture

composed of 10% carbon monoxide, 20% hydrogen, and 70% nitrogen started. The

impeller speed was varied from 0 to 2000 RPM. For the 0.5% rhodium catalyst, no

variation in conversion was noticed above an impeller speed of 750 rpm. The 70% nickel

catalyst showed a drop in conversion at speeds below 1750 RPM. From these tests it was

concluded that the reactor was perfectly mixed with the impeller speed at 2000 RPM. This

had been shown earlier by Hadjigeorghiou [171. Also, as noted by Hadjigeorghiou, there

existed a small temperature difference between the catalyst bed and the gas phase in the

reactor. Between temperatures of 300CC and 500'C, this temperature difference ranged

from 13°C to 21'C. It was later found that part of this difference was caused by the

thermocouples, which did not read the exact same temperature in the operating range of the

reactor. No other tests, such as residence time analysis, ect. were needed, since

Hadjigeorghiou had applied similar proceedures to confirm good mixing.

3.3 CSTR Loading

Loading the CSTR is one of the most critical steps in the experimental procedure.

Improper handling can lead to irreparable darnage to the reactor. Table 3.2 outlines the

steps required to properly assemble and disassemble the CSTR.

44

Table 3.2

Assembly / Disassembly Procedure

ASSEMBLY

a) Check all screws for tightness and inspect reactor parts for cracks and contaminants.

b) Inspect all tubing fittings for tightness and cracks.

c) With the bottom of the basket removed, drop catalyst pellets and alumina pelletsbetween the retaining screens. DO NOT force the pellets. Be certain to disperse thecatalyst pellets with alumina for good heat dispersion.

d) Place the catalyst retaining ring in the basket. DO NOT force it into place.

e) Place the basket horizontally on a table with the thermocouple hole at the top and shakethe basket horizontally to settle the pellets away from the thermocouple entrance.

f) Place the basket on the machined end of the dead volume insert, being certain that thescreen does not get bent when the thermocouple enters the basket. If the screen is bentthe basket must be emptied and the screen straightened. If this is not done the screenwill be caught in the impeller and the basket and thermocouples will be destroyed.

g) Place the bottom on the basket and secure it with screws.

h) While firmly grasping the magnetic drive unit and guiding the basket with your otherhand, lift the unit so it is vertical.

i) Place the reactor assembly in the pressure vessel. Be certain to keep the unit verticalwhile doing this or the dead volume insert may be bent or cracked. The reactor partsare ONLY 1/32" thick.

j) Install the pressure vessel bolts and tighten opposite bolts sequentially.

k) Connect the inlet line, cooling water lines, and thermocouple leads.

1) Pressure test the system to check for leaks.

DISASSEMBLY

a) Cool the reactor in nitrogen from its reaction temperature especially when working with

nickel catalysts to remove any traces of nickel carbonyl.

b) Follow the Assembly instructions in reverse order.

c) Place the magnetic drive unit in the wooden stand

45

3.4 Catalyst Testing

The catalyst testing facility is almost completely automated, except for the MFCs

which were set manually. For these studies the MACSYM 2 was used only to operate the

sampling valves and record temperatures from different parts of the unit (Appendix E. 1).

The large lag-time in the reactor temperature control loop made it impractical to control the

reactor temperature with the computer. As a result, experiments were arranged so that one

temperature was studied over a series of feed component partial pressures, each set

manually. This method of data acquisition saved time because the reactor would stabilize at

a steady state five times faster after a change in feed composition, than it would after a

change in temperature setpoint.

To obtain good kinetic data, the CSTR was operated so the conversion within the

reactor was very small, or differential. Operating at this low level of conversion (under

10%) allows the methanation reaction to dominate and suppresses the shift reaction. This

was important because the kinetics of the methanation reaction were of interest.

The testing procedures for the 0.5% Rh catalyst and the 70% Ni catalyst are similar,

yet different enough to describe them separately.

The 0.5% Rh catalyst was to be tested between 300'C and 5000 C at 50 0 C

increments. Since this catalyst was to be used in the first of a series of methanators, it was

desirable to test it and obtain kinetic data with and without steam in the feed stream. The

series of experimental i un: anc c'.'tlined in Tables 3.3 and 3.4.

46

Table 3.3

0.5% Rhodium CatalystStudy Without Steam

Run H2 to CO Flow Rate H2 FlowRate CO Flow Rate N2Number Ratio (scem) (sccm) (sccm)

1 2.0 200 100 1002 1.5 150 100 1503 1.0 100 100 2004 2.0 160 80 1605 1.5 120 80 2006 1.0 80 80 2407 2.0 120 60 2208 1.5 90 60 2509 1.0 60 60 28010 2.0 240 120 4011 1.5 180 120 10012 1.0 120 120 16013 1.5 210 140 5014 1.0 140 140 12015 1.5 234 156 1016 1.0 156 156 8817 1.0 176 176 4818 1.0 196 196 819 2.0 80 40 28020 1.5 60 40 30021 1.0 40 40 32022 2.0 40 20 34023 1.5 30 20 35024 1.0 20 20 360

After the CSTR was loaded, following the instructions in Table 3.2, it was purged

with nitrogen at 100 sccm for 20 minutes. All of the system furnaces were turned on and

the CSTR heated at a rate of 3°C per minute with hydrogen flowing at 50 sccm. At 10'C

below the desired operating condition, the reactant gas flow for a selected standard

condition was started. The total gas flow for all experimental runs was 400 sccm. The

CSTR attained steady state after 15 minutes and the standard condition was run for four

product samples. After the fourth sample, the feed composition was changed. The new

condition was run until four product samples were taken, then the composition changed

47

again. This process continued for three composition changes. Before the CSTR was shut

down, after the completion of several runs, the standard feed composition was measured

again. This data was used to determine if the catalyst deactivated, and if so, by how much.

This information was used to normalize the experimental data. After the standard run, all

reactant gases were shut off except for nitrogen, which flowed at 100 sccm until the reactor

and furnaces cooled to room temperature. Once cooled, the nitrogen flow was decreased to

20 sccm so that the catalyst remained in an inert environment until the next series of

experiments.

Table 3.4

0.5% Rhodium CatalystStudy With Steam

Run H2 to CO Flow Rate H2 Flow Rate CO Flow Rate H20 Flow Rate N2Number Ratio (sccm) (sccm) (sccm) (sccm)

1 2.0 160 80 80 802 1.5 120 80 80 1203 1.0 80 80 80 1604 2.0 120 60 60 1605 1.5 90 60 60 1906 1.0 60 60 60 2207 2.0 184 92 92 328 1.5 150 100 100 509 1.0 100 100 100 10010 1.0 120 120 120 4011 1.0 130 130 130 1012 2.0 40 20 20 32013 1.5 30 20 20 33014 1.0 20 20 20 34015 2.0 80 40 40 24016 1.5 60 40 40 26017 1.0 40 40 40 280

The 70% Ni catalyst was tested between 300'C and 500'C at 50'C increments.

This catalyst was to be used in the last methanator as a clean-up catalyst, and thus it was

tested with steam in the feed stream. Nickel catalysts coke extensively at hydrogen to

48

carbon monoxide ratios lower than three. It was expected that the steam in the feed would

reduce the coking so that good experimental data could be obtained. The series of

experimental runs are outlined in Table 3.5.

Table 3.5

70% Nickel CatalystStudy With Steam

Run H2 to CO Flow Rate H2 Flow Rate CO Flow Rate H20 Flow Rate N2Number Ratio (sccm) (sccm) (sccm) (sccm)

1 2.0 160 80 80 802 1.5 120 80 80 1203 1.0 80 80 80 1604 2.0 120 60 60 1605 1.5 90 60 60 1906 1.0 60 60 60 2207 2.0 184 92 92 328 1.5 150 100 100 509 1.0 100 100 100 100

10 1.0 120 120 120 4011 1.0 130 130 130 1012 2.0 40 20 20 32013 1.5 30 20 20 33014 1.0 20 20 20 34015 2.0 80 40 40 24016 1.5 60 40 40 26017 1.0 40 40 40 280

The daily operating procedure for the 70% Ni catalyst was the same as that for the

0.5% Rh catalyst except for one initial procedure. Before a new catalyst charge could be

used it had to be reduced to remove the small surface oxidation layer which the

manufacturer added for passivation purpose . The 0.5% Rh was not easily oxidized, and

heating to reaction temperature in hydrogen was sufficient enough to remove any oxides.

The 70% Ni catalyst was reduced by heating to 4000C with a hydrogen flow of 50 sccm

and holding it at 400'C for eight hours. After this period of time, the catalyst could be

49

either held in the reactor in nitrogen for future experiments, or used directly by adjusting

the reactor temperature to the desired reaction temperature.

To be certain the derived kinetic expressions accurately predicted the methanation

and shift kinetics over a broad range of operating conditions, data was needed at high

carbon monoxide conversions. For both the 0.5% Rh and 70% Ni catalysts several

experimental runs were done at each temperature, where the conversion of carbon

monoxide exceeded 30%, but was less than 70% to avoid equilibrium. The higher

conversions were achieved by increasing the catalyst loading and repeating several of the

runs outlined in Tables 3.3 to 3.5.

In addition to the kinetics, the durability of both catalysts had to be determined.

One lifetime study, of 100 hours duration, was performed at 400'C on the 0.5% Rh

catalyst. Lifetime studies of 300 hours duration at 300'C, 350'C, and 4000 C were made

on the 70% Ni catalyst. All lifetime studies were conducted with low H2/CO ratio feeds

and high carbon monoxide conversion.

50

CHAPTER 4

RESULTS AND DISCUSSION - 0.5% Rh

This chapter discusses the experimental results on the 0.5% Rh catalyst. In this

chapter the experimental procedure is reviewed and any deviations or difficulties included.

The methods of data analysis, the results without steam, the results with steam, the kinetics

expressions, and the results of the lifetime study are presented and discussed.

4.1 Review of Experimental Procedure

The experimental procedure for the testing of the 0.5% Rh catalyst remained the

same as described in Chapter 3 except the range of temperature was 400 to 500'C. This

change was made because of the very low activity of the catalyst at temperatures below

400'C. Since the catalyst was not to be used at temperatures below 4000C, the acquisition

of kinetic data in this range was not necessary.

The catalyst was reduced in hydrogen at 50 sccm while the reactor was heating to

the operation temperature at a rate of 3°C min. -1 . At first this reduction period was not

thought to be enough, so a different reduction method was tried. The catalyst was first

heated in nitrogen to 400'C then reduced with hydrogen at 50 sccm for four hours. The

activity was measured at a standard feed condition at 400'C. Another catalyst charge was

then reduced by the original method and the activity measured at 400C under the same

feed condition. This test showed no difference in initial activity, so the original method

was retained.

Maintenance to the system was minimal. Al] of the equipment operated well and

did not fail. Every ten reactor loadings the Swagelok fittings connecting the reactor to the

feed line had to be replaced. The fittings were damaged by a combination of heating-

51

cooling and assembly-disassembly cycles. Replacing these fittings reduced the danger of

leaks. The wire screen of the catalyst basket was replaced every four months. Loading

and unloading the basket caused the screen to distend out of shape, thus leading to fracture

after several runs. The basket was replaced before it broke to prevent possible damage to

the reactor during a run. Other routine maintenance included draining the water separators,

and calibrating the instruments.

The only equipment modification made to the system after the initial reconfiguration

was the addition of silica gel dryers after the water separators. These were necessary

because the separators did not remove all of the water from the product stream, especially

when water was added in the feed. Water in the analysis line to the GC changes the

volume of the sample loops and produces a larger CO 2 peak during analysis, thus

introducing inaccuracies.

4.2 Data Analysis

Manipulation of the data obtained from each experimental run was performed by an

Apple Macintosh Plus computer, using the Basic programming language. All experimental

data was entered via key board and stored in data files on floppy disks. Using the

programs listed in Appendix E.2 & E.3, the data was stored, manipulated, and printed.

These programs performed all of the material balances and calculated the rates of

methanation. The data for all of the experimental runs for the 0.5% Rh catalyst are given in

Appendix C.

4.2.1 Definitions

The results presented in Appendix C contain the following definitions. Conversion

of CO is the moles of CO converted per mole of CO in the feed. The yield of methane is

52

moles of methane produced per moles of CO fed. The correction factor is the percent of

original catalyst activity exhibited by the catalyst sample, during a particular run, taking

100% as the activity measured on new catalyst at a standard feed condition. A new

standard activity was determined for each new catalyst loading, at a standard feed

condition, for the temperature at which that loading was run. For example, if a series of

runs were measured at 400'C, the standard activity was found at 400'C on the fresh

catalyst at a standard feed condition. Each day the catalyst loading was reused, the

standard feed condition was run both at the beginning of the day and at the end of the day.

In this way the catalyst activity was known and any deactivation detected. Any deactivation

which occurred over the course of a day was assumed to be linear. The mean of the

deactivation over a certain run time was determined, and used to calculate the percentage of

original activity in the catalyst sample. It should be noted that the data appearing in

Appendix C was adjusted to account for any deactivation which occurred over an

experimental run.

4.2.2 Sources of Deactivation

The formation and elimination of iron carbonyl from the reactor feed stream is

discussed in Section 2.2. This cause of deactivation was detected at the start of the

experimental work, and eliminated as a source of catalyst deactivation.

After the iron carbonyl poisoning problem was corrected, a contaminant in the

catalyst support was suspected. The suspicion was justified by a magnetic measurement

which revealed trace amounts of iron in the alumina support [30]. As pointed out by Mills

[4], iron very' strongly catalyzes the formation of carbon (Reactions {1.61 and {1.71) and

a- sho\\ . in Figure 1.6. the formation of carbon ik enhanced by the temperature and H2'CO

ratios used during the experimental runs. Despite this trace iron contamination, the catalyst

was used, but strict attention to catalyst deactivation was necessary.

53

Carbon formation was observed at all temperatures studied. The carbon was very

light and caused little fouling at temperatures above 400°C. Below 400C the rate of

carbon formation increased as temperature lowered. Formation of carbon, coupled with the

catalyst's low activity at temperatures below 400°C, made the study of the kinetics in the

300 to 400C range very difficult and was avoided.

After the completion of the experimentation on the 0.5% Rh catalyst, work by

Patterson [31] revealed cata'yst sintering in the 400 to 500C temperature range. In

addition to the correction for deactivation, an additional correction was made to account for

sintering. The rates at different temperatures were adjusted to the rhodium dispersion at

500C by means of surface areas measured with dynamic hydrogen adsorption. These

values are given in Table 4.1.

Table 4.1

Surface Areas of 0.5% Rh 1161

Temperature Rhodium Surface Area

(°C) m2g- 1 (Rh)

300 214400 211500 194600 170

4.3 Results Without Steam in the Feed

The first series of experiments on the 0.5% Rh catalyst were conducted without

steam in the feed. A series of experimental runs (Table 3.3) were made at 400'C, 450°C,

and 500'C. Appendix C contains the tabulated results of these runs. In Figures 4.1 to 4.6

54

100.5% Rh (400 C)

o 1:1 H2/CO8 - 1.5:1 H2/CO

" 2:1 H 2 /CO

oil o

000- 2 ° 0

0-'

0.0 0.1 0.2 0.3 0.4 0.5 0.6

H 2 Partial Pressure (atm)

Figure 4.1Methanation Rate versus H2 Partial Pressure 4000C (No Steam in Feed)

100.5% Rh (400 C)o 1:1 H 2 /CO *

8 . 1.5:1 H2 /CO* 2:1 H 2 /CO

.2'6 . oS0 0

00* 0

4- 0

0 0

0--.0.0 0.1 0.2 0.3 0.4 0.5

CO Partial Pressure (atm)

Figure 4.2Methanation Rate versus CO Partial Pressure 400'C (No Steam in Feed)

55

8-

0.5% Rh (450C) e0 1: 1 H 2 /CO

10' 6 1.5:1 H2/CO 0* 2:1 H 2 /CO o

. ==0 0g

000 0 U

0.0 0.1 0.2 0.3 0.4 0.5 0.6


Figure 4.3Methanation Rate versus H2 Partial Pressure 450'C (No Steam in Feed)

8-

0.5% Rh (450 C)0 1:1 H 2 /CO *

• 6 * 1.5:1 H2/COx 2:1 H 2 /CO 0

C 0

00

eQ oU 0

o2 0

0

0.0 0.1 0.2 0.3 0.4 0.5


Figure 4.4Methanation Rate versus CO Partial Pressure 450'C (No Steam in Feed)

56

6-0.5% Rh (500 C)

5 0 1:1 H2/CO0 1.5:1 H2/CO o

r 4 2:1 H2/CO o= 40

- .- 0

000U

0 +- - -0.0 0.1 0.2 0.3 0.4 0.5 0.6

H2Partial Pressure (atm)

Figure 4.5Methanation Rate versus H2 Partial Pressure 500'C (No Steam in Feed)

6-0.5% Rh (500 C)

-c 5- 0 1:1 H2 /CO

." , 9 1.5:1 H 2/CO 0x a 2:1 H 2 /CO 0 0

C 4 0

3- 0

+2

0 00

00

0.0 0.1 0.2 0.3 0.4 0.5


Figure 4.6

Methanation Rate versus CO Partial Pressure 500'C (No Steam in Feed)

57

1.5o0.5% Rh (400 C)

0 1:1 H 2 /CO* 1.5:1 H2 /CO

X g 2:1 H2 /CO

1.0 0 0

0 0

0.500 00 •O

o

0

0.0 I V I I I

0.0 0.1 0.2 0.3 0.4 0.5 0.6

H2 Partial Pressure (atm)

Figure 4.7

Shift Rate versus H2 Partial Pressure 400C (No Steam in Feed)

1.5-0.5% Rh (400 C) 0 1:1 H2 /CO" 1.5:1 H2 /CO

1.0 • 2:1 H 2 /CO

0 0

MU 0

0.5Ib 0 0

0.0*

0.0 I , ,

0.0 0.1 0.2 0.3 0.4 0.5


Figure 4.8

Shift Rate versus CO Partial Pressure 400C (No Steam in Feed)

58

3-0.5% Rh (450 C)0 1:1 H2 /CO 0

0 1.5:1 H2/COm 2:1 H2/CO 0

2 00

00 0

000 1oei

0 I * .

0.0 0.1 0.2 0.3 0.4 0.5 0.6


Figure 4.9

Shift Rate versus H2 Partial Pressure 450'C (No Steam in Feed)

3-0.5% Rh (450 C)0 1:1 H2/CO 00 1.5:1 H2ICO

" 2 s 2:1 H2/CO o

0

0

00 U

0 * I *

0.0 0.1 0.2 0.3 0.4 0.5


Figure 4.10Shift Rate versus CO Partial Pressure 450'C (No Steam in Feed)

59

3-0.5% Rh (500 C)0 1:1 H2 /CO 0 o

* 1.5:1 H 2 /CO 0=X 2:1 H 2 /CO"2 2 0 0

M, co 0

0 00.0 0

0 0

0.0 0.1 0.2 0.3 0.4 0.5 0.6


Figure 4.11

Shift Rate versus H2 Partial Pressure 500'C (No Steam in Feed)

o0.5% Rh (500 C)0 1:1 H 2 /CO 0

" 0 1.5:1 H 2 /CO 0X 2 a 2:1 H2/CO

e e

0-0* * I *

0.0 0.1 0.2 0.3 0.4 0.5CO Partial Pressure (atm)

Figure 4.12

Shift Rate versus CO Partial Pressure 500'C (No Steam in Feed)

60

the rate of methanation is plotted as a function of H2 and CO partial pressures. Figures 4.7

to 4.12 show the rate of shift.

From the plots of methanation rate versus partial pressure, one can see several

trends. The rate of methanation has a near first-order dependence on the partial pressure of

H 2. A similar first-order dependence can also be seen with the CO partial pressure, but

with different curves for a different H2/CO ratio, with 1:1 having the least slope and 2:1 the

greatest. This feature shows the extent to which higher relative CO concentrations inhibit

the formation of methane. Plots of shift rate versus CO partial pressure show a near first-

order dependence, while plots versus H2 partial pressure have a lot of scatter, caused by

the different H 2/CO ratios, which leaves no observable trends.

4.4 Results With Steam in the Feed

The second set of experiments on the 0.5% Rh catalyst were made with steam in the

feed at a 1:1 ratio with CO. A series of experimental runs (Table 3.4) were conducted at

400'C, 450°C, and 500'C. The tabulated results of these runs are in Appendix C. In

Figures 4.13 to 4.18 the rate of methanation is plotted as a function of H2 and CO partial

pressures. Figures 4.19 to 4.24 show the rate of shift.

With steam in the reactor feed, the same trends observed without the steam were

also observed. At this point a comparison can be made between the two sets of

experimental runs. As seen in Figures 4.25 to 4.42 the addition of steam to the feed stream

lowered the rate of methanation. This result is expected because water is a product of the

methnation reaction.

3H 2 + CO 4 CH14 + H20 {1.10}

61

4 0.5% Rh (400 C)Steam in Feed

0 1:1 H2/CO • 3 * 1.5:1 H2/CO

o 2:1 H2 /CO

O~)° O

CD

o0S0

0

0

0.0 0.1 0.2 0.3 0.4 0.5


Figure 4.13Methanation Rate versus H2 Partial Pressure 4000C (Steam in Feed)

0.5% Rh (400 C)Steam in Feed

., 0 1:1 H 2 /COI= 3 * 1.5:1 H 2 /CO

m 2:1 H 2 /CO U

0* 0

U0 0

* 00

.. I

0.0 0.1 0.2 0.3 0.4


Figure 4.14Methanation Rate versus CO Partial Pressure 400'C (Steam in Feed)

62

4 0.5% Rh (450 C)Steam in Feed0o 1:1 oH2 (C

3 * 1.5:1 H2/COC a 2:1 H2/CO

o0

cu0 o

0-

0.0 0.1 0.2 0.3 0.4 0.5


Figure 4.15

Methanation Rate versus H2 Partial Pressure 450'C (Steam in Feed)

0.5% Rh (450 C)Steam in Feed0 0 1:1 H 2 /CO

3 9 1.5:1 H2/CO oC- a 2:1 H 2 /CO *

.. 0.-C

2- 0

OQ 0

00

0I * II

0.0 0.1 0.2 0.3 0.4


Figure 4.16

Methanation Rate versus CO Partial Pressure 450'C (Steam in Feed)

63

4 0.5% Rh (500 C)0 Steam in Feed

0 1:1 H 2 /CoI= 3 o 1.5:1 H2/CO

C m 2:1 H2/COM 0C

0

Figur 4.1

0@

00

00

0.0 0.1 0.2 0.3 0.4 0.5H2 Partial Pressure (atm)

Figure 4.17Methanation Rate versus H2 Partial Pressure 500'C (Steam in Feed)

4 0.5% Rh (500 C)Steam in Feed0 1:1 H2/CO

X 3 1.5:1 H2 /CO* 2:1 H2 /CO o

2- 0

0

-1

0.0 0.1 0.2 0.3CO Partial Pressure (atm)

Figure 4.18Methanation Rate versus CO Partial Pressure 500'C (Steam in Feed)

64

1.0- 0.5% Rh (400 C)Steam in Feed

, 0.8 0 1:1 H2 /COx 1.5:1 H 2 /CO

2:1 H2/COU " 0.6-

0 0

0 10C~0.4- 0

0

o- 0

0.2 °

0.0 , ,0.0 0.1 0.2 0.3 0.4 0.5


Figure 4.19

Shift Rate versus H2 Partial Pressure 400'C (Steam in Feed)

1.0 0.5% Rh (400C)

Steam in Feed0.8 0 1:1 H 2 /CO

.x 1.5:1 H2/CO2:1 H 2 /CO

"' 0.6-0

S0.4 %

0.2 -

0.0- , " ,

0.0 0.1 0.2 0.3 0.4


Figure 4.20Shift Rate versus CO Partial Pressure 400'C (Steam in Feed)

65

4 0.5% Rh (450C)o Steam in Feed0

0 1:1 H2/CO 03 0 1.5:1 H2/CO a

0 2:1 H2/CO 0

0 02 -

0

0.

0-0.0 0.1 0.2 0.3 0.4 0.5


Figure 4.21

Shift Rate versus H2 Partial Pressure 450°C (Steam in Feed)

4 0.5 % Rh (450 C)

Steam in Feed0 1:1 H2I/CO 0

3 0 1.5:1 H2/CO 0

. o 2:1 H2/CO 0

2-

0.0 0.1 0.2 0.3 0.4


Figure 4.22

Shift Rate versus CO Partial Pressure 450'C (Steam in Feed)

66


4 0 1:1 H 2 /CO o 0

, 1.5:1 H2fCO. 2:1 H2 /CO S

f3-

0

0U

0

! I

0.0 0.1 0.2 0.3 0.4 0.5


Figure 4.23Shift Rate versus H2 Partial Pressure 500'C (Steam in Feed)


, 4 0 1:1 H2/CO 0 o. 1.5:1 H 2 /COo 2:1 H2/CO S

0- I

0.0 0.1 0.2 0.3


Figure 4.24Shift Rate versus CO Partial Pressure 500'C (Steam in Feed)

67

0.5% Rh (400 C)1:1 H2/CO Feedo No Steam 0

3 e Steam in Feed0

000


Figure 4.25Comparison of Methanation Rate versus H2 Partial Pressure

With and Without Steam 400'C

0.5% Rh (400 C)1:1 H2/CO Feed

c 0o No Steam" Steam in Feed

0

0

0

0.0 0.1 0.2 0.3


Figure 4.26Comparison of Methanation Rate versus CO Partial Pressure


68

0.5% Rh (450 C)1:1 H2 /CO Feed

4 0 NoSteam 0

* Steam in FeedC0

0

0 *0

oS

0-0

0.0 0.1 0.2 0.3 0.4H 2 Partial Pressure (atm)


With and Without Steam 450 0C

5 0.5% Rh (450 C)O 1:1 H 2/CO Feed

00- 4 o No Steam

9 Steam in Feed 0

2- 0

C0

001 o

00

0.0 0.1 0.2 0.3 0.4



With and Without Steam 4500C

69

3 0.5% Rh (500 C)1:1 H2 /CO Feed 0o No Steamo Steam in Feed

2-cS

00

0 1 $




3 0.5% Rh (500 C)1:1 H2/CO Feed 0

o No Steamo Steam in Feed

2

0

0

0.0 0.1 0.2 0.3 0.4




70

5 0.5% Rh (400 C)1.5:1 H2:/CO Feed 0

'- 4 o No Steamo Steam in Feed

Xo

.33

0

0-0

01 I '

0.0 0.1 0.2 0.3 0.4H2 Partial Pressure (atm)



5 0.5% Rh (400 C)1.5:1 H 2/CO Feed 0

- No Steamo Steam in Feed

0

00

0.0 0.1 0.2 0.3CO Partial Pressure ( atm)


With and Without Steam 4000 C

71

0.5 % Rh (450 C)1.5:1 H2 /CO Feed

- 4 o No Steam 0e Steam in Feed

2 oE5 E

00

0-I I

0.0 0.1 0.2 0.3 0.4




5 0.5% Rh (450 C)1.5:1 H2/CO Feed

E 4 o No Steam 0

x * Steam inFeed

3- 0

2- 0

1 o

0

0 I |




72

3 0.5% Rh (500 C) 0

1.5:1 H2/CO Feed 0o No Steama Steam in Feed

2

o000, 1

00 oa0- I'I *

0.0 0.1 0.2 0.3 0.4




3- 0.5% Rh (500C) 0

1.5:1 H2 /CO Feedo No Steam

x e Steam in Feed2-

0

~Ll 0

00 8

0.05 0.10 0.15 0.20 0.25CO Partial Pressure (atm)



73

8 0.5% Rh (400 C)

2:1 H2/CO Feedo No Steam 0

6 * Steam in Feed

0

- 000

0 I I

0.0 0.1 0.2 0.3 0.4 0.5




8 0.5% Rh (400C)2:1 H2 /CO Feed

o No Steam 06 e Steam in Feed

0 0

4Z.7 0 0

0-0

2o 2

0I * I

0.0 0.1 0.2 0.3




74

4 0.5% Rh (450C) 02:1 H2/CO Feeda No Steam

3 * Steam in Feed

0 o

- 1

0-0.0 0.1 0.2 0.3 0.4


Figure 4.39Comparison of Methanation Rate versus H 2 Partial Pressure


4 0.5% Rh (450 C)2:1 H2/CO Feed

o No Steam3 e Steam in Feed

00

c~1 0

0.0 0.1 0.2




75

0.5% Rh (500 C)2:1 Hj/CO Feed 0•

0 No Steam

x Steam in Feed

2

"

00

00

0.0 0.1 0.2 0.3 0.4 0.5H 2 Partial Pressure (atm)



3 0.5% Rh (500 C)o 2:1 H2 /CO Feed 5

o No Steam0 Steam in Feed

2-

0

000




76

which is slowed by product inhibition. It can also be seen that the H2/CO ratio did not

affect the relative amount by which the rate of methanation dropped when steam was added

to the feed. As the temperature increased, the relative drop in the rate of methanation, with

the addition of steam to the feed, decreased. This effect could be caused by an increase in

the rate of the water-shift reaction,

CO + H20 CO 2 + H2 {1.12}

with the increased water concentration. This in turn increases the H2/CO ratio through the

consumption of CO and the production of H2. The increase in the H2/CO ratio favors the

formation of methane { 1. 10} thus decreasing the relative rate difference. This hypothesis

is supported by the fact that the amount of CO 2 in the product increased greatly with the

addition of steam. It should also be noted that the amount of CO2 produced per mole of

CH 4 increased greatly when steam was added to the feed. This ratio increased with

temperature, but increased more rapidly in the runs where steam was present in the feed to

the reactor. The above facts show the importance of the water-shift reaction { 1.12} at high

temperatures and high water partial pressures.

Figures 4.43 to 4.60 show the effect of steam on the rate of the water-shift Reaction

{1.12}. As with the rate of methanation, the relative difference between the rates of shift

with and without steam is not affected by the H2 /CO ratio, but by temperature. Increase in

the rate of shift with the addition of steam to the feed is evident at temperatures above

400'C. At a constant temperature and partial pressure of CO the rate of shift decreases

with an increase in the H2/CO ratio. As noted earlier, Reaction {1.10} is favored by an

increase in the H2!CO ratio. Increased consumption of CO by Reaction {1.10} at high

H2/CO ratios reduces the amount available for Reaction { 1. 121, thus causing a decrease in

the rate of Reaction { 1.1 2}.

77

2.0 - 0.5% Rh (400 C)

1:1 H2/CO Feedo No Steam

1.5 * Steam in Feed4.-

* 1.0"

o

" 0.5 0 00 00

0.0 1 ,

0.0 0.1 0.2 0.3H2 Partial Pressure (atm)

Figure 4.43Comparison of Shift Rate versus H2 Partial Pressure


2.0 0.5% Rh (400 C)1:1 H2.'CO Feed

o No Steamx 1.5 * Steam in Feed

1.0-

3 0.-

~0.5 0

0 0

0.0 1 "

0.0 0.1 0.2 0.3


Figure 4.44Comparison of Shift Rate versus CO Partial Pressure


78

0.5% Rh (450 C)1:1 H2 /CO Feed

o No Steam3 * Steam in Feed 0

0 0S 0

0.0 01020.3 0.4H2 artalPressure (atm)

Fiue4.45Comarionof Shf aeversus H2 Partial Pressure

With and Without Steam 450°C

4.0.5% Rh (450 C)

S 1:1 H2/CO Feed

00

o No Steam-X3 * Steam inFeed 5

- 0

00 0. 0

2 Pata rssr am

4 - 0

• 0

0 0 o00

0* * 00 0

o0

0.0 0.1 0.2 0.3 0.4CO Partial Pressure (atm)



79

4 0.5% Rh (500C)1:1 H2/CO Feedo No Steam

3 e Steam in Feed

2-

"~ 0

* 0

0000I * I

0.0 0.1 0.2 0.3 0.4




0.5% Rh (500 Q1:1 H2 /CO Feedo No Steam

x 3 9 Steam in Feed 0

S0

L 0 0 0

0

00

0-0.0 0.1 0.2 0.3 0.4




80

2.0 0.5% Rh (400 C)O1.5:1 H2 /CO Feed

o No Steam1.5 o Steam in Feed

4.-

1.0

0 0OS60.5- 0 0 0

8SS

0.0,0.0 0.1 0.2 0.3 0.4




2.0- 0.5% Rh (400 C)1.5:1 H2/CO Feedo No Steam

1.5 * Steam in Feed

1.0

0 0

3 0.5-

0.0 ,0.0 0.1 0.2 0.3




81

3 0.5% Rh (450 C)1.5:1 H2/CO Feed

o No Steam9 Steam in Feed

2-

0)0 o

0

0

00.0 0.1 0.2 0.3 0.4




0.5% Rh (450 C)1.5:1 H2 /CO Feed

o No Steam* Steam in Feed S

2-

00! 0

0

0-



With and Without Steam 450 0C

82

4 0.5% Rh (500 C)1.5:1 H2 /CO Feed

o No Steam3- Steam in Feed

U 0

01 00

00

0 5 I I"

0.0 0.1 0.2 0.3 0.4


Figure 4.53Comparison of Shif! Rate versus H2 Partial Pressure


4-0.5% Rh (500 C)1.5:1lH 2CO Feed

o No Steam

x 3 e Steam in Feed

2-

0.05 0.10 0.15 0.20 0.25

CO Partial Pressure (aim)


With and Without Steam 500°>C

83

0 H 5~~ aiama * ll n* I I

2.0 0.5% Rh (400 C)o2:1 H2 /CO Feed

o No Steam1.5 - Steam in Feed

1.0

0* 80.5-

0.0 0.1 0.2 0.3 0.4 0.5




2.0 0.5% Rh (400 C)

2:1 H2 /CO Feedo No Steam

1.5 * Steam in Feed

1.0-

0

" 0.5 -

08

0.0,0.0 0.1 0.2 0.3




84

2 0.5%c Rh (450 C)

2:1 H2/CO Feeda No Steam

. * Steam in Feed

S0C0

00o3 o

o

00




2 0.5% Rh (450 C)

2:1 H2 /CO Feedo No Steam* Steam in Feed

• 0

0

0

0*0.0 0.1 0.2




85

3 0.5% Rh (500 C)2:1 H 2/CO Feed

o No Steam e Steam in Feed

-2

00

00o 0 0

00

0.0 0.1 0.2 0.3 0.4 0.5




3 0.5% Rh (500 C)c 2:1 H2 /CO Feed

o No Steam* Steam in Feed

:E 2-

M 0" 1 o

U 0

0

0o 4 r

0 * I

0.0 0.1 0.2 0.3




86

4.5 Kinetic Expressions

A search of the literature shows that the application of rhodium to methanation has

been studied, but this work was done at lower temperatures and at H2/CO ratios higher

than of interest here. An example is the work of Vannice [32,331, who studied the

synthesis of hydrocarbons from hydrogen and carbon monoxide mixtures over Group VIII

metals. One catalyst he looked at was I % Rh on A120 3. He conducted experiments over a

range of H2/CO ratios at 265'C. For the rate expression a power law was chosen of the

form,

rCH4 = Ae-EmIRT PH2X Pco Y (4.1)

where rcH4 is the molecules of CI.4 formed per metal site per second. At 275°C Vannice

observed a first-order dependence on the H2 concentration and a zero order dependence on

the CO concentration. For this work no steam was mixed with the feed. Vannice's work

pointed out that rhodium did catalyze the methanation reaction, but his rate expression

could not be used for comparison because of the dangers involved in extrapolating a power

law expression out of the temperature and pressure range under which it was developed.

Initial forms of the kinetic expression were obtained using a linear regression

program, which used the IMSL subroutine RLONE, to calculate the constants of a

linearized Langmuir-Hinshelwood expression, which was thought to be of the right form.

Different expressions were tried until one was found which fit the data from all of the runs

over the temperature range studied. The final form of the kinetic expression was

determined by Richardson [ 161.

For the 0.5% Rh catalyst, a Langmuir-Hinshelwood expression was obtained for

the rate of methanation of the form,

87

-4 k-, Kro Pco PNRM -+-KoPc mole min-Ig(cat) "1 (4.2)

Without steam in the feed, the rate constant kM and the adsorption constant Kco fit the

Arrhenius expressions,

kM = 7.94 x 10-2 e -2519/RT (4.3)

Kco = 4.58 x 10-2 e 23795/RT (4.4)

With steam added to the feed in a 1:1 ratio with CO, the constants fit the Arrhenius

expressions,

kM = 5.57 x 10-2 e -31086/RT (4.5)

Kco = 1.92 x 10-5 e 71268/RT (4.6)

For the water-shift reaction, {1.12} two separate rate equations were obtained for the cases

of no steam in the feed and steam in a 1:1 ratio with CO. For the case of no steam in the

feed a first-order dependence on H20 was observed of the form,

--.4

=k 1 PH2O mole min-1g(cat)-I (4.7)

ksI = 45.18 e -38228'RT (4.8)

For the case of steam in the feed, a first-order dependence on H20 was also observed of

the form,

Rs= ks2 PH2O mole min-ig(cat) -l (4.9)

kS2 3 .2 5x ]0 3 e -7836S RT (4.10)

with all P's in atmospheres and R = 8.314 J mole-IK "1

88

These rate equations apply only in the temperature range 400 to 500'C. All of these

rate expressions were found to fit the experimental data very well. The regression

coefficients for Equations (4.2), (4.7), and (4.9) appear in Table 4.2. Comparisons of the

calculated rates of methanation and shift can be seen in Tables 4.3 and 4.4 respectively.

Table 4.2

Regression Coefficients(* Steam in Feed)

Equation Regression Coefficient

-+ km Kc 0 Pco PH,RM -( I + Kco Pco )2 0.9854 (4.2)

0.9692 *

Rs = ks PH20 0.8923 (4.7)-4Rs = kS2 PH20 0.9716 * (4.9)

Table 4.3

Comparison of Calculated Methanation Rate to Experimental Results(* Steam in Feed)

Temperature PH2 PCO kM Kco Rate x 103 Rate x 103

(°C) Calculated Experimental

400 0.223 0.242 0.0506 3.218 2.779 2.534400 0.179 0.193 0.0506 3.218 2.142 1.921400* 0.346 0.238 0.0215 6.520 1.775 1.708400* 0.089 0.043 0.0215 6.520 0.238 0.349450 0.329 0.232 0.0522 2.398 3.947 4.035450 0.267 0.136 0.0522 2.398 2.586 2.645450* 0.190 0.184 0.0316 2.702 1.332 1.463450* 0.050 0.043 0.0316 2.702 0.147 0.161500 0.129 0.088 0.0537 1.856 0.835 0.849500 0.047 0.046 0.0537 1.856 0.183 0.175500* 0.220 0.134 0.0442 1.255 1.197 1.165500* 0.103 0.082 0.0442 1.255 0.385 0.375

89

Table 4.4

Comparison of Calcu'ated Shift Rate to Experimental Results(* Steam in Feed)

Temperature PH20 ks Rate x 103 Rate x 103

(OC) Calculated Experimental

400 0.022 0.04880 1.074 0.919400 0.005 0.04880 0.244 0.231400* 0.207 0.00269 0.557 0.453400* 0.101 0.00269 0.272 0.367450 0.010 0.07826 0.783 0.761450 0.002 0.07826 0.187 0.174450* 0.250 0.00709 1.773 1.881450* 0.050 0.00709 0.355 0.452500 0.001 0.11807 0.118 0.172500 0.016 0.11807 1.889 1.864500* 0.242 0.01647 3.986 3.899500* 0.045 0.01647 0.741 0.611

Since it was not possible to derive a suitable rate expression with one set of

constants, two separate sets of rate and equilibrium constants for the methanation and shift

rate equations are necessary. The expressions must thoroughly describe the methanation

and shift kinetics for the cases of no steam in the feed and steam in a 1:1 ratio with CO.

Several forms of the Langmuir-Hinshelwood expression were tried, but none correlated

with the experimental data. A similar situation arose in the study of CO 2 reforming on the

0.5% Rh catalyst by Paripatyadar [I]. Here again two separate sets of constants were

needed to describe the kinetics when steam was absent or present in the reactor feed.

4.6 Kinetic Expressions at High Conversions

Most of the experimental runs were done at low conversions so the kinetics of the

methanation reaction { 1.10) could be studied. Equations (4.2) to (4.10) all reflect kinetics

90

at low conversions and must be modified to describe kinetics at high conversion. To

accomplish tis additionA data was taken at high conversions with steam in the feed at a 1:1

ratio v,1 th CO (Appendix C).

Near equilibrium, the rate of methanation is slowed. To account for this, reverse

terms were needed in the kinetic expressions, resulting in the equations[ 16],

PCH4 PHO (4. 1)RM=RM[I KMPcoPH2

K-- PCO2 PH23

PC~O, PH,Rs= RS 1 - Ks Pco PH20 (4.12)

where KM and Ks are the equilibrium constants of the methanation and shift reactions

respectively. The above equations gave higher rates than measured at high conversions.

At near complete conversion large amount, of CH4 and CO2 are present. The presence of

high concentrations of these gases would inhibit the methanation and shift reactions

respectively. This inhibition is not accounted for in Equations (4.11) and (4.12). To

provide for this, inhibition terms were added to the denominators of the rate equations and

the constants fitted to the high conversion data. For the case of steam in the feed the rate of

methanation is expressed,

PCHK PH2 0K., Pco PH, 3

RM = kN KCO PH2 Pco (I + Kco Pco + KMCH4 PCH4 + KMC02 PCO2) 2 (4.13)

and the rate of shift,

Pco, PH,K, PCO PH2O

Rs= ks PH20 (1 + KSCH4 PCH4 + KScO 2 Pco 2) (4.14)

91

with all of th: constants the same as Equations (4.3), (4.4), and (4.8) along with

KMCH4 = 0.552 e13743/RT (4.14)

KMCO 2 = 0.559 e 10700 ,RT (4.15)

KSCH4= 0.974 e1374 3/RT (4.16)

K = 0.978 e] 0700 'RT. (4.17)

Ddta was not available to fit the constants for the case without steam, but it is reasonable to

use the additional constants from the steam case to get,

PCH4 PH20K,, Pco PH, 3

= kNI Kco PH2 Pco (1 + Kco Pc KMCH4 PCH4 + KMC2 PC0 (4.18)

PC02 PH-)

1 KS Pco PH(O

Rs = ks PH2O (I + KSCH 4 PCH4 + KsCo 2 Pc0 2 ) (4.19)

which were later compared with data from the integral reactor of the Screening Unit [ 141

and found to be in good correlation [161.

4.7 Lifetime Study

One lifetime stud) was performed on the 0.5% Rh catalyst. The problem with the

iron contamination in the support was known, but it was still desired to test the catalyst

performance. For this study the reactor was loaded with 1.5238g of catalyst and run for

100 hours at 400'C and 400 sccm of feed, composed of 30% CO, 30% H20, 30% H2.

92

and 10% N2. Representative data appears in Appendix F. At completion of the 100 hours,

the catalyst was checked for physical damage. As seen in Figure 4.6i, the catalyst showed

a slight deactivation. This was thought to have been caused by the iron impurity in the

alumina support. Physical examination of the catalyst revealed a very light deposit of

carbon on the catalyst surface. Without the impurity in the alumina support, it is felt that

the catalyst would have a very long lifetime and remain free of carbon.

1.0-0.90 Lifetime Study0.9. 0.5% Rh (400 C)

, 0.8- 100 Hours

0.7= 0.6

0.5

0.4

0.3

0.20.10.0 . .

0 20 40 60 80 100

Time (hr)

Figure 4.61

Lifetime Stud) 4000C

93

CHAPTER 5

RESULTS AND DISCUSSION - 70% Ni

This chapter focuses on the experimental results for the 70% Ni catalyst. The

experimental procedure is reviewed and any deviations or difficulties included.

Experimental results, kinetic expressions, and results of the lifetime study are presented

and discussed.

5.1 Review of Experimental Procedure

The experimental procedure for the testing of the 70% Ni catalyst remained the

same as described in Chapter 3, except experiments were not conducted at 450 0 C due to

carbon formation on the catalyst at high temperatures.

An eight hour reduction period was believed to be too long, so periods of four and

six hours, at 400'C and H, flow of 50 sccm, were tried. In both cases the reduction

period proved too short as evidenced by low initial catalyst activity. Periods longer than

eight hours were tried, but failed to increase initial catalytic activity. The eight hour

reduction period proved necessary for proper catalyst reduction.

Maintenance practices for the systemn are Aell established, and are described in

Chapter 4. During this study no additional modifications were made to the equipment.

5.2 D:it2 Analysis

Processing of the experimental data remained the same. All of the data for

experimental runs on the 70% Ni catalyst are tabulated in Appendix D.

94

5.2.1 Definitions

Data presented in Appendix D use the same definitions of conversion, yield and

correction factor. These definitions are clearly stated in Section 4.2.1.

5.2.2 Sources of Deactivation

The formation and elimination of iron carbonyl from the reactor feed was discussed

in Section 2.2. This cause of deactivation was detected at the start of the experimental

work on the 0.5% Rh catalyst and eliminated.

Formation of carbon on the 70% Ni catalyst made study of kinetics difficult. As

mentioned in section 3.4, it was hoped that the addition of steam to the feed stream would

reduce the amount of carbon formed. Bartholomew [6] found that higher partial pressures

of steam in methanator feed gases reduced, and even eliminated the formation of carbon.

Addition of steam to the feed eliminated carbon fouling at 300 and 350"C, but the effect

greatly decreased at higher temperatures. Little deactivation was noticed, and carbon

formation limited to the darkening of the pellet surface at 300 and 350C. At 4000 C the

pellets had a light carbon coat and lost their physical strength after only 42 hours of

operation. This problem was more severe at high CO partial pressures (0.3 atm) and less

severe at lower partial pressures (0.05 atm). At 500^C and 26 hours of operation, the

pellets were very brittle and had a fuzz) la)er of filamentous carbon on the surface. At

both 400'C and 500°C the catalyst did not decrease in activity, despite the carbon deposited

on the surface, but increased in activity after 40 and 24 hours of operation respectively.

The structure of the pellet was weakened by the formation of carbon. It was thought that

the carbon formation exerted pressure on the support and broke the pellet, thus exposing

more active metal, which in turn caused an increase in activity. More catalyst activity is

always desired, but the destruction of the alumina support in the process cannot be

tolerated.

95

Weakening of the catalyst support has been attributed to the formation of

filamentous carbon [6,34,35]. According to Bartholomew [6], this is one of four types of

carbon which are formed by the Boudouard reaction { 1.7}. Filamentous, or vermicular

carbon form at the rear of the metal particle and form a polymeric carbon filament which

lifts the metal particle off of the support surface. This continues until the metal particle

becomes encapsulated in inactive carbon. This polymeric filament growth exerts pressure

on the catalyst support from within the pores. This causes the support to weaken and even

break. Bartholomew (61 also points out that the formation of filamentous carbon is

retarded and even absent in H2 rich environments. Since the experimental runs were

conducted at low H 2/CO ratios, formation of filamentous carbon on the 70% Ni catalyst

was enhanced.

At both 400 and 5000 C, the catalyst was operated for 10 hours without severe

deactivation (< 10%) and no observable damage to the support. Hayes et al. [351 point out

that the formation of carbon on a catalyst surface is initially a slow process, but once started

proceeds at a very fast rate. The 10 hour operation time was not long enough to allow the

formation of carbon to proceed at a very fast rate. A comparison of the feed and product

compositions with the Sigma 115 GC showed no measurable carbon loss. Deactivation

required the catalyst to be changed and reduced after three experimental runs. Replacing

the catalyst after every three runs insured that the quality of the data would be maintained.

All catalyst deactivation was carefully monitored as described in Section 4.2.1.

5.3 Experimental Results

Experimental runs on the 70% Ni catalyst were conducted with steam in the feed at

a 1: 1 ratio with CO. Experiments without steam were not conducted because of the severe

carbon formation on the catalyst in the absence of steam. Experimental runs (Table 3.5)

96

were conducted at 300C, 350*C, 400°C, and 5001C. The tabulated results appear in

Appendix D. Figures 5.1 to 5.8 show the rate of methanation plotted as a function of H2

and CO partial pressures. The rate of shift is shown in Figures 5.9 to 5.16.

The data from the experimental runs on the 70% Ni catalyst show trends which are

similar to the 0.5% Rh catalyst (Section 4.3). Methanation rates pass through a maximum

then decrease and the shifts rate increase with temperature, though not as dramatically as

with rhodium. The 70% Ni catalyst has a low selectivity for methane, as evidenced by the

higher relative rate of the water-shift reaction.

5.4 Kinetic Expression

A search of the literature produced several studies of nickel catalysts on alumina

supports, but as in the case of the 0.5% Rh catalyst, these studies were not conducted at

low H2/CO ratios or in the temperature range of interest. The main reason used by several

researchers for not operating below a H2/CO ratio of three was the formation of carbon on

the catalyst. For the sake of comparison a few kinetic expressions for the rate of

methanation are presented.

Akers and White [36] conducted a study of methanation kinetics on a nickel

kieselguhr catalyst in a temperature range of 300 to 350'C, at H2/CO ratios between 1.2

and 4. The rate equation which best fit their data was,

Pco PH23

r =C H (5.1)(A + B PCo + DPCo + EPCH4 )4

where A,B,D, and E are constants.

97

4- 70% Ni (300 C)Steam in Feed 0o 1:1 H 2 /CO

3 0 1.5:1 H2 1COo 2:1 H2/CO 0

2 ,

. 1 0

0

0-

0.0 0.1 0.2 0.3 0.4 0.5


Figure 5.1

Methanation Rate versus H2 Partial Pressure (300'C)

70% Ni (300 C)Steamin Feed * *0 1:1 H 2 /CO

3-n

X3 1.5:1 H2/COC w 2:1 H2/CO 0

2- 0

0 1 0

0.0 0.1 0.2 0.3


Figure 5.2Methanation Rate versus CO Partial Pressure (300'C)

98

5- 70% Ni (350 C)Steam in Feed

4 0 1:1 H2 /CO* 1.5:1 H 2/CO* 2:1 H2JCO. 3" o

3- 0.

2- -

0

0

0.0 0.1 0.2 0.3 0.4 0.5


Figure 5.3Methanation Rate versus H2 Partial Pressure (350'C)

5 70% Ni (350 C)0 Steam in Feed

4 0 1:1 H2/CO 0

0 1.5:1 H2/COCU 2:1 H 2 /CO

2 - 0

0 0

0.0 0.1 0.2 0.3


Figure 5.4Methanation Rate versus CO Partial Pressure (350°C)

99

70% Ni (400 C)Steam in Feed

--E 4 0 1:1 H 2/CO 00 1.5:1 H2/CO oo U 2:1 H 2 /CO

j3-0*0

0.0 0.1 0.2 0.3 0.4 0.5H2z Partial Pressure (atm)

Figure 5.5Methanation Rate versus H2 Partial Pressure (400'C)

5-70% Ni (400 C)Steam in Feed

S4- 0 1:1 H2 /CO0 1.5:1 H2 ICO0

C a 2:1 H2/CO

o2-

00

010

0.0 0.1 0.2 0.30.


Figure 5.Methanaton Rate versus CO Partal Pressure (400C)

00

0. 0.110.2/0.COPatil'rssre(am

Figure 5.

Mehaaio Rt rssCO Partial Pressure (C

100

4- 70% Ni (500 C)Steam in Feed0 1:1 H2/CO

3 o 1.5:1 H2/COC 2:1 H2/CO .

0- 0 0 1

0.0 0.1 0.2 0.3 0.4 0.5


Figure 5.7Methanation Rate versus H2 Partial Pressure (5000C)

00

4''

0- 0

x~~ 0 : 2C

-- 8. 1: 12C 1

0.0 .1 0.2 0.3


Figure 5.8Methanation Rate versus CO Partial Pressure (500'C)

101

• n wm a una m ln I UI 0

70% Ni (300 C)Steam in Feed o

- 4 0 1:1 H2/Co. 1.5:1 H2/CO 0U 2:1 H2 /CO

0

001 0 0

0.0 0.1 0.2 0.3 0.4 0.5H2 Partial Pressure (atm)

Figure 5.9Shift Rate versus H2 Partial Pressure (300'C)

5 70% Ni (300C) 0Steam in Feed 0

- 4 0 1:1 H 2 /CO

0 1.5:1 H 2 /CO 0

U 2:1 H2/COS 3

0

0


Figure 5.10

Shift Rate versus CO Partial Pressure (3000C)

102

7-70% Ni (350 C)Steam in Feed o0 1:1 H2 /CO 0

5 5"* 1.5:1 H2/CO. n 2:1 H2/CO 0

~...S 4-07

0 U

00'-1 0 n

et em

010.0 0.1 0.2 0.3 0.4 0.5


Figure 5.11Shift Rate versus H2 Partial Pressure (350*C)

70% Ni (350 C)Steam in Feed

- 0 1:1 H 2 /CO. 5 0 1.5:1 H2/CO

a 2:1 H2/CO 0

0 n

0

21 n0 0

- 1

0.0 0.1 0.2 0.3

CO Partial Pressure (atm)Figure 5.12

Shift Rate versus CO Partial Pressure (350*C)

103

8 70% Ni (400 C)

Steam in Feed O0

0 1:1 H 2 /CO 06 o 1.5:1 H2/CO

a 2:1 H 2 /CO 0

00

00

0-0

0.0 0.1 0.2 0.3 0.4 0.5


Figure 5.13Shift Rate versus H2 Partial Pressure (400'C)

8- 70%7cNi (400CQO Steam in Feed

0

11 H2 /CO 0x6- o 1.5:1 H2 ICO

. 2:1 H2 ICO 0

0

2- 0s

0-0

0 I

0.0 0.1 0.2 0.3


Figure 5.14

Shift Rate versus CO Partial Pressure (400'C)

104

10- 70% Ni (500 C)O Steam in Feed

0 0o 8 o 1:1 H 2 /CO o

* 1.5:1 H 2 /CO* 2:1 H2 /CO 0

00

4- 0:(o u

u0

0 i

0-I I I

0.0 0.1 0.2 0.3 0.4 0.5


Figure 5.15

Shift Rate versus H2 Partial Pressure (500"C)

10' 70% Ni (500 C)Steam in Feed

8- 1:1 H2 /CO

x ; 0 1.5:1 H2 /CO 0Z- 6 2:1 H2 /CO

~f6

4000

0 I I

0.0 0.1 0.2 0.3


Figure 5.16Shift Rate versus CO Partial Pressure (500'C)

105

Lee et al. [37] found a methanation kinetic expression for a nickel catalyst over the

300 tc 450'C temperature range but in a H2/CO ratio range greater than three. The

equation they found to fit their data was,

k PHR0.5 Pco( I + K 2 PH2 + K 3 PCH 4 (5.2)

The same form of the above expression was found by Bienstock et al. [381 in his work on

the synthesis of high Btu gas.

The above expressions were derived from experimental data taken under conditions

which were close to the conditions used for the 70% Ni catalyst study, while other work on

methanation with nickel catalyst was not. A good summary of this work can be seen in a

paper by Vannice [39].

The kinetic expression for the 70% Ni catalyst was developed in the same manner

as that of the 0.57 Rh catalyst, with the final form determined by Richardson 116]. A

Langmuir-Hinshelwood expression, similar to the one found for the 0.5% Rh catalyst, was

fit to the data. The methanation rate fit the equation,

-4 kNI Kc 0 KH, PCO PH,RN, - (1 + KCO Pco-+ KI 2 PH 2 ) (5.3)

with,

kM = 20.9 e-44135/RT (5.4)

Kco = 1.01 e12694iRT (5,5)

K. 2 = 2.41 x 10-4 e51821'RT. (5.6)

The rate of shift fit-4Rs = ks PH2O (5.7)

ks = 0.168 e-12156 /RT (5.8)

106

with all P's in atmospheres and R = 8.314 J mole-IK 1 .

These rate equations apply in the temperature range of 300 to 500'C. These

equations were found to fit the data fairly well. Tables 5.1 and 5.2 show a comparison of

the calculated and experimental rates

Table 5.1

Comparison of Calculated Methanation Rate to Experimental Results

Temperature PH2 Pco km Kco KH2 Rate x 103 Rate x 103

(OC) Calculated Experimental

300 0.186 0.177 0.00198 14.496 12.736 2.03 1.88300 0.140 0.132 0.00198 14.496 12.736 1.44 1.37350 0.195 0.184 0.00417 11.706 5.322 2.21 1.81350 0.286 0.136 0.00417 11.706 5.322 2.46 2.33400 0.194 0.182 0.00786 9.758 2.532 2.09 2.16400 0.147 0.136 0.00786 9.758 2.532 1.44 1.46500 0.208 0.057 0.02180 7.277 0.764 0.91 0.98500 0.455 0.205 0.02180 7.277 0.764 3.98 3.14

Table 5.2

Comparison of Calculated Shift Rate to Experimental Results

Temperature PH20 ks Rate x 103 Rate x 103

(°C) Calculated Experimental

300 0.200 0.013 2.60 1.88300 0.148 0.013 1.92 2.06350 0.197 0.016 3.15 3.39350 0.154 0.016 2.46 2.03400 0.197 0.019 3.74 3.98400 0.146 0.019 2.77 3.04500 0.188 0.025 4.70 4.97500 0.228 0.025 5.70 5.22

107

5.5 Kinetic Expressions at High Conversions

As for the 0.5% Rh catalyst, the kinetic expression for the 70% Ni catalyst needed

to be modified to account for higher concentrations of products at high conversions. This

adjustment was treated in the same manner as for the rhodium catalyst (Section 4.6). The

rate of methanation and the rate of shift for the high conversion experiments fit

PCH4 PH20km KH2 KCO PH 2 PCO 1] " KM PCO PH2 (.

RM =(1 + KH 2 PH2 + KCO lco + KMp PCH4 + KMp PCO2 ) (5.9)

ks PH2O 11 - PCO, PH2 ..]Ks Pco PHO= (1 + Ksp PCH 4 - KSp PCO 2 ) (5.10)

with the additional constants,

KMp = 5.59 x 10-3 e26 4 14/RT (5.11)

Ksp = 7.75 e6345/RT. (5.12)

Equations 5.9 and 5.10 give an empirical fit over a narrow range of temperature. It

is important to point out that these equations apply only from 300 to 350'C which is the

practica. ", crating range of this catalyst.

5.6 Lifetime Study

The 70% Ni catalyst was tested with three lifetime studies at 300, 350, and 400'C

to check the durability and resistance to carbon formation. Representative data from these

studies appears in Appendix F.

108

The first study at was conducted at 300'-C. The reactor was loaded with 6.0425g

of 70% Ni catalyst, reduced for eight hours as described in Section 3.4, and run for 300

hours with a feed flow of 400 sccm composed of 28.5% H2 , 19% CO, 19% CO2 9.5%

CI-I4 , 19% H20, and 5% N2. The reactor operated at a CO conversion of about 87% for

300 hours with little deactivation (Figure 5.17). Examination of the catalyst revealed no

carbon formation or damage to the alumina support.

The second lifetime study was conducted at 400'C. The reactor was loaded with

5.3017 g of catalyst, reduced, and run for 300 hours with the same feed mixture used at

300'C. The reactor operated at about 80% CO conversion for 300 hours with little

deactivation (Figure 5.19). Examination of the catalyst revealed a thin layer of filamentous

carbon on the surface of the pellets. The pellets were also brittle. This test revealed that the

70% Ni catalyst could not be used at 400'C even at low CO partial pressures.

The last lifetime study was conducted at 350°C. This study would reveal if the

70% Ni catalyst can be used between 300 and 350'C. The reactor was loaded with

4.4609g of catalyst, reduced, and run for 300 hours with the same feed mixture used at

300°C. The reactor operated at a CO conversion of about 86% for 300 hours with little

deactivation (Figure 5.18). Examination of the catalyst revealed no carbon formation or

damage to the support.

109

1.00 .9 -P V0.8-

U 0.7 Lifetime Study

o 0.6 70% Ni (300 C)0.5 300 Hours- 0.5

0.4

~0.30.20.10.0 ,

0 100 200 30OTime (hr)

Figure 5.17Lifetime Study 300'C

1.0-0.9 . _ _ .. _ _ _: _ r 4 - -, . - . . .

0.8S0.7 Lifetime Sudy

€ 0.6 70% Ni (350 C)0.5 300 Hours

= 0.4

0.30.20.10.0 1

0 100 200 300Time (hr)

Figure 5.18Lifetime Study 350 0C

110

1.0~0.90.8- -- -0.7

c= 0.7 Lifetime Study

0 70% Ni (400 C)

0.5 300 Hours" 0.4

@0.3

0.2

0.10.0 ,

0 100 200 300

Time (hr)

Figure 5.19Lifetime Study 4001C

111

CHAPTER 6

CONCLUSIONS AND RECOMMENDATIONS

This study investigated the kinetics of the methanation reaction on 0.5% Rh and

70% Ni catalysts under conditions where the hydrogen to carbon monoxide ratio is near

one. The kinetic expressions for both the methanation and shift reactions were developed.

The expressions for the 0.5% Rh catalyst are applicable in the range of 400 to 5000C and

those for 70% Ni in the 300 to 350 0C range. In these ranges the expressions accurately

describe the reaction kinetics and will be suitable for reactor design.

The 0.5% Rh catalyst was found suitable for use in the exothermic portion of

Chemical Energy Transmission Systems (CETS), which use CO 2 reforming of methane for

the endothe,,nic reaction. The catalyst has a high activity at temperatures above 400'C with

a high selectivity for methane. Lifetime studies demonstrated the durability of this catalyst

at 400'C, and showed no deactivation which could not be attributed to iron impurities in

the feed or alumina support.

70% Ni is well suited for low temperature methanation at H2/CO ratios near one.

Nickel has a higher activity and is cheaper than rhodium. This makes it ideal for use in a

low temperature isothermal reactor, to complete conversion, in the methanation section of a

solar based CETS. The durability and resistance to carbon formation of the 70% Ni

catalyst were shown in lifetime studies at 300 and 350'C.

Further studies on the 0.5% Rh catalyst may provide insight into the interaction of

steam in the reaction mechanism, and allow the determination of a single expression to

describe the reaction kinetics.

The isothermal CSTR was shown to gi\e accurate data which is easy to analyze.

Its use reduced the number of assumptions which must be made, thus reducing inaccuracy

in the kinetic expressions.

112

Use of copper and copper alloys, which do not contain catalytic metals, in the

construction of the reactor and tubing prevented the formation of coke at H2/CO ratios near

one. This eliminated experimental error due to loss of carbon to coke formation.

Aluminum Silicon Bronze (CDA #642) was the alloy used in the CSTR.

Dual element thermocouples allow temperature measurements to be made, for both

temperature controllers and the process control computer, at the same location using only

one probe. They allow independent operation, free of electrical interference which is

caused when two instruments share a common probe.

If the CSTR is to be used for studies at total flow rates higher than 400 sccm, mass

flow controllers with a higher flow capacity will be needed.

An Analog Output Card for the MACSYM 2, to control the mass flow controllers,

would allow for complete automation of the Catalyst Screening Unit.

113

REFERENCES

1] Paripatyadar, S.,"Cyclic Operation of Sodium Heat-Pipe, Solar Reformers," Ph.D.,Dissertation, Dept. of Chem. Eng., Univ. of Houston (1987).

12] Harth, R., and Ahl, U., Interdisc. Sci. Rev 6(3), 221 (1981).

[31 Van Hook, J., Catal. Rev. Sci. Eng., 21(1), 1-51 (1980).

[41 Mills, G.H., and Steffen, F.W., Catal. Rev. Sci. Eng., 8, 159-210 (1973).

[5] Richardson, J.T., "Principles of Catalyst Development," Plenum Press, New York(1988) In press.

[6] Bartholomew, C.H., Catal. Rev. Sci. Eng., 24(1), 67-112 (1982).

[7] Richardson, J.T., Paripatyadar, S.A., Shen, J.C., AIChE Journal, 34(5) 743-52(1988).

[8] McCrary, J.H., McCrary, G.E., Chubb, T.A., Simmons, D.E., Solar Energy, 29(2),141-51 (1982).

[9] Pearce, R., Patterson, W.R., "Catalysis and Chemical Processes," John Wiley andSons, New York, (1981).

[10] DeMaria, G., D'Alessio, L., Coffari, L., Paolucci, M., Tiberio, C.A., Solar Energy,35(5), 409-16 (1985).

[111 Greyson, M., "Catalysis," Vol. 4, P. Emmett. ed., Reinhold, New York, (1956).

[121 Anderson, R.B., "Catalysis," Vol 4. P. Emmett. ed., Reinhold, New York, (1956).

[13] Vannice, M.A., "Catalysis: Science and Technology," Vol.3, J.A. Anderson andM. Boudart, ed.s, Springer-Verlag, New York (1982).

[141 Richardson, J.T., Cullinane, M.B., Unpublished Work.

[15] Cullinane, M.B.,"The Effect of Calcining Conditions on Nickel Catalyzed Fischer-

Tropsh Synthesis," M.S. Thesis, Dept. of Chem. Eng., Univ. of Houston (1983).

[16] Richardson, J.T., Cullinane, M.B., Keehan. D., In preparation.

[17] Hadjigeorghiou, G.A., "A CSTR Me?,,urement of High Pressure CatalyticMethanation," M.S. Thesis, Dept. of Chem. Eng., Univ. of Houston (1975).

[181 Torres-Acosta, I.L., "Computer Automated Testing of Nickel Catalysts for Fischer-Trupsh Synthesis," M.S. Thesis. Dci), . of CheM. Eng., Univ. of Houston (1983).

[19] Doraiswamy, L.K., Tajbl, D.G., Catal Rev.- Sci. Eng., 7, 177-219 (1975).

[20] Autoclave Engineers, Inc., "Technical Data Sheet #751," Pennsylvania (1970).

[211 Tylan Corporation, "Mass Flow Controller Instructions Manual," California (1981).

114

[221 Schay, Z., Lazar, K., Mink, J., Guczi, L., J. of Catalysis, 87, 179-195 (1984).

[23] Shao, R., Personal Communication, Dept. of Chem. Eng., Univ. of Houston(1987).

[24) Valco Instruments Co., "Mult-Functional 10-Port Valve," Texas.

[25] Perkin Elmer Corporation, "Instructions, Model Sigma I GasChromatograph,"Connecticut (1980).

[26] Perkin Elmer Corporation, "Instructions, Sigma Series Console," Connecticut(1980).

[271 Perkin Elmer Corporation, "Instructions, Molel Sigma 115 Gas Chromatograph,"Connecticut (1981).

[28] Purcell, J.E., Ettre, L.S., J. of Gas Chromatography, Feb., 69-71 (1965).

[29] Analog Devices Corporation, "MACSYM 2 User's Programming Guide,"Massachussets (1981).

[30] Shao, R., Personal Communication, Dept. of Chem. Eng., Univ. of Houston(1987).

[31] Patterson, ED., "Sintering of Rhodium Catalyst," M.S. Thesis, Dept. of Chem.Eng., Univ. of Houston (1988).

[32] Vannice, M.A., J. of Catalysis, 37, 449-61 (1975).

[33] Vannice, M.A., J. of Catalysis, 37, 462-73 (1975).

[34] Hayes, R.E., Thomas, W.J., Hayes, K.E., J. of Catalysis, 92, 312-26 (1983).

135] Hayes, R.E., Thomas, W.J.,"Catalysis on the Energy Scene," S. Kaliaguine andA. Mahay, ed.s, Elsevier, New York (1984).

[36] Akers, W.W., White, R.R., Chem. Eng. Progress, 44, 553 (1948).

[37] Lee, A.L., Feldkirchner, H.L., Tajbl, D.G., Am. Chem. Soc., Div. Fuel rhem.,Prepr., 14,126 (1970).

[38] Hausverger, A.L., Knight, C.B., Atwood. K., "Methanation of Synthesis Gas,"L. Seglin, ed., American Chemical Society, Washington, D.C. (1975).

[39] Vannice, M.A., Cat. Rev. Sci. Eng., 14(2), 153-91 (1976).

115

APPENDIX A

CALIBRATION CURVES

116

APPENDIX A. I

MASS FLOW CONTROLLER CALIBRATION CURVES

117

CALIBRATION CURVE HYDROGEN

200-

160

140

120

100

0-iU. 80

60

40

20-

0~0 20 40 60 80 100 120 140 160 180 200

DIGITAL OUTPUT

118

CALIBRATION CURVE HYDROGEN AUX.

200

180

'Co

140

12c

L)°(100

0-j 80

60

40

20

00 20 40 60 80 100 120 140 160 180 200

DIGITAL OUTPUT

119

CALIBRATION CURVE NITROGEN

200

180

160 -

140 -

120

t

100

0.-j 80

60

40

20

0

0 20 40 60 80 100 120 140 160 180 200

DIGITAL OUTPUT

120

CALIBRATION CURVE NITROGEN AUX.

200-

1 80

160

140

120 -

C.)100

0 ~8c

60

40

0

0 20 40 60 80 100 120 140 160 180 200

DIGITAL OUTPUT

121

CALIBRATION CURVE CARBON DIOXIDE

200 !

180

160

140

120

C-)

U100

0J-1 80-

60

40

20

0

0 20 40 60 80 100 120 140 160 180 200

DIGITAL OUTPUT

122

CALIBRATION CURVE CARBON MONOXIDE

200 - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

180-

160-

140

120

0

06

40-

20

0~0 20 40 60 80 100 120 140 160 180 200

DIGITAL OUTPUT

123

CALIBRATION CURVE METHANE

200

180

160

140

120

100

0-1 0iU.

60

40-

20-

0-0 20 40 60 80 100 120 140 160 180 200

DIGITAL OUTPUT

124

CALIBRATION CURVE FEED SAMPLE

30 -

25-

20-

U, 15-

0

10

5

0 *0 5 10 15 20 25 30

DIGITAL OUTPUT

125

APPENDIX A.2

SYRINGE PUMP CALIBRATION CURVE

126

Appendix A.2

Conversion of Water to Steam

Feed: Deionized water (23°C, 1 atm)

Product: Steam (105'C, 1 atm)

Ig Water (23°C, 1 atm) = 1.00244 cc

1.00244 cc Water (23°C, 1 atm) = 104343 cc Water (100°C, 1 atm)

At 1000C, I atm: 1.04343 cc Water = 1672.24 cc Steam

1672.24 cc Steam (100 0C, 1 atm) = 1694.65 cc Steam (105°C, 1 atm)

Using the Idea] Gas Law

1694.65 cc Steam (105 0C, I atm) = 1224.1 cc Steam (0°C, 1 atm)

Ig Water (23°C, 1 atm) = 1224.1 cc Steam (0°C, I atm)

127

CALIBRATION CURVE SYRINGE PUMP

240-

220

200-

180

1 60

140

1200-j U. ~100

80

60

40-

20-

0~0 100 200 300 400 500 600 700 800 900 1000

DIGITAL OUTPUT

128

APPEND B

CHROMATOGRAPFHC METOD

129

I. 4

F! NA L Y-cZE R kCs-13NTROL

NJTEMP 5mr-v~ *7flLiF 4 4 , r

LO A B 4.44 C AAu

N11A Di'N TfEIP,TII&E 1488 A#

mnira PR^^uDnd WD , Iir u* .C

" RSCALE 4 a

%of-#-t 4 -7. el fl IVf -y 7 P

c-i'#% - I' I 0 V a . d %AI08

i.tit4 n, ebn9T 0L W0.f58 FLO 0.aOR r e- P K A.8 325 315

NT ~AME CARB^N flo .,L

1.53 02. e 800.0600 HYD*ROGEN0%.6 .1 .""498 460.0600 NITROGEN

3.5 8.5380 &a v88 CARBON MONOXIDE4r.rtm n.c7c 208.80 JIETHAHE

A A. -V 3.2 vu faa uo~CRO DIOXIDEQS NO LT .1T6RU

ATTNC~RT-DE8'r6 5 88

T~E DEV'ICEION NAME

1 - EXT'r v ! P*UOL RE"-v~ 44 sr- -,-r-RE46- A C vi REc

2 .. b r- Q~ -!IPJ "U0.2 -TER SET ZERG

130

APPENDIX C

EXPERIMENTAL RUN DATA 0.5% Rh CATALYST

131

TABLE OF EXPERIMENTAL RESULTS0.5% RHODIUM CATALYST

RUN NUMBER * 1 2 3 4 5

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (9r)* .075 .075 .075 .075 .075FEED RATE (SCCM) * 382 382 382 380 380C04VERSION CO * .127 .09 .052 .115 .086YIELD OF CH4 * .114 .078 .045 .108 .074RATE METH. x 1000 * 6.465 4.443 2.534 4.896 3.336(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .761 .642 .42 .298 .561(MOL/qCAT-MIN)

FEED PARTIAL PRESSURES (ATM)

H2 * .5 .375 .25 .4 .3CO * .25 .25 .25 .2 .2N2 * .25 .375 .5 .4 .5CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0

PRODUCT PARTIAL PRESSURES (ATM)

H2 * .443 .332 .223 .352 .266CO * .231 .237 .242 .185 .188N2 * .265 .39 .511 .418 .515CH4 * .03 .02 .011 .023 .015C02 * .004 .003 .002 .001 .003H20 * .027 .017 .01 .021 .013********4 k-r4 4

CORRECTION FACTOR * 1 1 1 .982 .964

132

TABLE OF EYPERIMENTAL RESULTS0.5% RHODIUM CATALYST

RUN NUMBER * 6 7 8 9 10

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (9r)* .075 .075 .075 .075 .075FEED RATE (SCCM) * 380 380 380 380 380CONVERSION CO * .051 .106 .082 .05 .136YIELD OF CH4 * .043 .095 .07 .042 .122RATE METH. x 1000 * 1.921 3.204 2.37 1.417 8.253(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .393 .4 .393 .285 .956(MOL/qCAT-MIN) *


H2 * .2 .3 .225 .15 .6CO * .2 .15 .15 .15 .3N2 * .6 .55 .625 .7 .1CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .179 .267 .199 .134 .534CO * .193 .138 .141 .144 .28N2 * .61 .566 .638 .709 .108CH4 * .009 .015 .011 .006 .039C02 * .002 .002 .002 .001 .005H20 * .007 .013 .009 .005 .035*************************** ********************************

CORRECTION FACTOR * .947 .9 .882 .865 .853

133


RUN NUMBER * 11 12 13 14 15

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (9r)* .075 .075 .075 .075 .075FEED RATE (SCCM) * 380 380 380 380 380CONVERSION CO * .098 .059 .106 .111 .058YIELD OF CH4 * .084 .049 .092 .096 .n49RATE METH. x 1000 * 5.71 3.336 7.255 8.428 3.853(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .936 .637 1.116 1.384 .767(MOL/9CAT-MIN) *


H2 * .45 .3 .525 .585 .35CO * .3 .3 .35 .39 .35N2 * .25 .4 .125 .025 .3CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .398 .266 .463 .518 .313CO * .285 .291 .334 .375 .341N2 * .263 .412 .134 .027 .311CH4 * .027 .015 .034 .04 .018C02 * .004 .003 .005 .007 .004H20 * .022 .012 .029 .034 .014


134


RUN NUMBER * 16 17 18 19 20

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (9r)* .075 .075 .075 .179 .179FEED RATE (SCCM) * 380 380 380 379 379CONVERSION CO * .061 .06 .06 .185 .14YIELD OF CH4 * .052 .051 .052 .159 .112RATE METH. x 1000 * 4.62 5.043 5.715 1.497 1.055(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .785 .875 .919 .247 .264(MOL/qCAT-MIN) *


H2 * .39 .44 .49 .2 .15CO * .39 .44 .49 .1 .1N2 * .22 .12 .02 .7 .75CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .346 .395 .44 .16 .122CO * .382 .433 .485 .084 .088N2 * .229 .126 .021 .723 .767CH4 * .021 .023 .027 .016 .011C02 * .004 .004 .004 .003 .003H20 * .018 .019 .022 .014 .009


135


RUN NUMBER * 21 22 23 24 25

TEMPERATURE (C) * 400 400 400 400 350CATALYST WEIGHT (gr)* .179 .179 .179 .179 .471FEED RATE (SCCM) * 379 379 379 379 383COtWERSION CO * .097 .154 .126 .087 .078YIELD OF CH4 * .073 .123 .093 .057 .072RATE METH. x 1000 * .686 .582 .438 .269 .657(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .231 .146 .158 .14 .048(MOL/gCAT-MIN) *


H2 * .1 .1 .075 .05 .5CO * .1 .05 .05 .05 .25N2 * .8 .85 .875 .9 .25CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .082 .084 .063 .043 .464CO * .092 .043 .044 .046 .239N2 * .812 .861 .883 .905 .259CH4 * .007 .006 .005 .003 .019C02 * .002 .002 .002 .001 .001H20 * .005 .005 .003 .001 .017

CORRECTION FACTOR * .96 .91 .895 .88 1

136


RUN NUMBER * 26 27 28 29 30

TEMPERATURE (C) * 350 350 350 350 350CATALYST WEIGHT (gr)* .471 .471 .193 .193 .193FEED RATE (SCCM) * 383 382 391 391 391CONVERSION CO * .072 .084 .134 .16 .178YIELD OF CH4 * .069 .078 .128 .154 .174RATE METH. x 1000 * .752 .563 2.286 2.087 1.574(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .035 .046 .12 .086 .04(MOL/qCAT-MIN) *


H2 * .6 .4 .79 .6 .4CO * .3 .2 .198 .15 .1N2 * .1 .4 .013 .25 .5CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .562 .366 .754 .558 .361CO * .29 .189 .18 .132 .085N2 * .104 .413 .013 .262 .518CH4 * .022 .016 .027 .024 .018C02 * .001 .001 .001 .001 0H20 * .021 .015 .025 .023 .018


137


RUN NUMBER * 31 32 33 36 37

TEMPERATURE (C) * 350 350 350 350 350CATALYST WEIGHT (gr)* .193 .193 .193 .193 .193FEED RATE (SCCM) * 391 391 391 390 390CONVERSION CO * .085 .093 .173 .116 .127YIELD OF CH4 * .079 .084 .155 .108 .117RATE METH. x 1000 * 1.747 1.526 .704 1.463 1.053(MOL/qCAT-MIN)RATE SHIFT x 1000 * .144 .163 .078 .113 .091(MOL/qCAT-MIN)


H2 * .735 .6 .2 .45 .3CO * .245 .2 .05 .15 .1N2 * .02 .2 .75 .4 .6CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .706 .57 .18 .416 .272Co * .233 .188 .042 .137 .089N2 * .021 .207 .762 .413 .614CH4 * .02 .017 .008 .017 .012C02 * .002 .002 .001 .001 .001H20 * .018 .016 .007 .015 .011


138

TABLE OF EXPERIMENTAL RESULTS0.5Y RHODIUM CATALYST

RUN NUMBER * 38 39 40 41 42

TEMPERATURE (C) * 350 450 450 450 450CATALYST WEIGHT (9r)* .193 .096 .096 .096 .096FEED RATE (SCCM) * 390 389 389 389 388CONVERSION CO * .134 .139 .12 .146 .119YIELD OF CH4 * .118 .118 .103 .132 .098RATE METH. x 1000 * .533 5.322 3.721 7.185 2.645(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .073 .992 .638 .745 .572(MOL/qCAT-MIN) *

FEED PAPTIAL PRESSURES (ATM)

H2 * .15 .5 .4 .6 .3CO * .05 .25 .2 .3 .15N2 * .8 .25 .4 .1 .55CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .135 .443 .357 .527 .267CO * .044 .229 .183 .278 .136N2 * .81 .266 .417 .109 .567CH4 * .006 .031 .021 .043 .015C02 * .001 .006 .004 .004 .003H20 * .005 .025 .018 .039 .012

CORRECTION FACTOR * .878 1 .974 .931 .864

139


RUN NUMBER * 43 44 45 46 47

TEMPERATURE (C) * 450 450 450 450 450CATALYST WEIGHT (9r)* .096 .096 .096 .096 .096FEED RATE (SCCM) * 388 387 388 389 389CONVERSION CO * .099 .077 .112 .114 .12YIELD OF CH4 * .078 .058 .081 .089 .094RATE METH. x 1000 * 1.404 .522 2.942 4.035 5.098(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .388 .174 1.109 1.141 1.44(MOL/qCAT-MIN) *


H2 * .2 .1 .3 .375 .45CO * .1 .05 .2 .25 .3N2 * .7 .85 .5 .375 .25CH4 * 0 0 0 0 CC02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .182 .093 .266 .329 .396CO * .092 .046 .184 .232 .28N2 * .711 .855 .517 .392 .265CH4 * .008 .003 .017 .023 .03C02 * .002 .001 .006 .007 .008H20 * .006 .002 .01 .017 .021


140


RUN NUMBER * 48 49 50 51 52

TEMPERATURE (C) * 450 450 450 450 450CATALYST WEIGHT (9r)* .096 .096 .096 .096 .096FEED RATE (SCCM) * 389 388 388 389 389C:OIVERSION CO * .128 .081 .086 .091 .134YIELD OF CH4 * .1 .054 .059 .063 .106RATE METH. x 1000 * 6.353 1.944 2.643 3.424 7.468(MOL/qCAT-MIN)RATE SHIFT x 1000 * 1.744 .979 1.256 1.5 2.007(MOL/qCAT-MIN) *


H2 * .525 .2 .25 .3 .585CO * .35 .2 .25 .3 .39N2 * .125 .6 .5 .4 .025CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .462 .177 .219 .261 .515CO * .328 .188 .235 .284 .368N2 * .134 .613 .515 .416 .027CH4 * .038 .011 .015 .02 .045C02 * .01 .006 .007 .009 .012H20 * .027 .005 .008 .011 .033


141


RUN NUMBER * 53 54 55 56 57

TEMPERATURE (C) * 450 450 450 450 450CATALYST WEIGHT (qr)* .096 .096 .096 .096 .144FEED RATE (SCCM) * 389 389 389 389 388CONVERSION CO * .095 .092 .098 .097 .147YIELD OF CH4 * .065 .065 .068 .069 .105RATE METH. x 1000 * 4.096 4.614 5.42 6.107 1.891(MOL/qCAT-MIN) *RATE SHIFT x 1000 * 1.902 1.915 2.407 2.521 .761(MOL/qCAT-MIN) *


H2 * .35 .39 .44 .49 .225CO * .35 .39 .44 .49 .15N2 * .3 .22 .12 .02 .625CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .307 .342 .387 .432 .19CO * .332 .373 .422 .474 .132N2 * .314 .232 .128 .021 .645CH4 * .024 .027 .032 .036 .016C02 * .011 .011 .014 .015 .007H20 * .013 .016 .018 .021 .01


142

TABLE OF EXPERIMENTAL RESULTS

0.5% RHODIUM CATALYST

RUN NUMBER * 58 59 60 61 62

TEMPERATURE (C) * 450 450 450 450 450CATALYST WEIGHT (gr)* .144 .144 .144 .144 .144FEED RATE (SCCM) * 388 388 388 388 388CONVERSIO4 CO * .131 .102 .079 .099 .116YIELD OF CH4 * .09 .068 .04 .061 .076RATE METH. x 1000 * 1.09 .409 .242 .731 1.381(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .487 .207 .234 .463 .716(MOL/gCAT-MIN) *


H2 * .15 .075 .05 .1 .15CO * .1 .05 .05 .1 .15N2 * .75 .875 .9 .8 .7CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .129 .067 .046 .087 .124CO * .089 .045 .046 .091 .136N2 * .764 .881 .904 .81 .716CH4 * .009 .003 .002 .006 .012C02 * .004 .002 .002 .004 .006H20 * .005 .002 0 .002 .006


143


RUN NUMBER * 63 64 65 66 67

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (9r)* .1 .1 .1 .1 .1FEED RATE (SCCM) * 389 389 389 388 388CONVERSION CO * .12 .102 .122 .096 .099YIELD OF CH4 * .089 .074 .06 .067 .073RATE METH. x 1000 * 3.886 2.587 4.512 2.904 2.542(MOL/SCAT-MIN) *RATE SHIFT x 1000 * 1.345 .947 1.864 1.241 .879(MOL/gCAT-MIN) *


H2 * .5 .4 .6 .375 .3CO * .25 .2 .3 .25 .2N2 * .25 .4 .1 .375 .5CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .461 .372 .562 .343. .269CO * .23 .185 .278 .234 .186N2 * .262 .412 .105 .388 .515CH4 * .023 .015 .027 .017 .015C02 * .008 .006 .011 .007 .005H20 * .015 .01 .016 .01 .01

CORRECTION FACTOR * 1 .916 .846 .572 .586

144


RUN NUMBER * 68 69 70 71 72

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (9r)* .1 .1 .1 .1 .1FEED RATE (SCCM) * 388 388 388 388 388C:0YERSION CO * .106 .09 .078 .066 .071YIELD OF CH4 * .072 .066 .05 .038 .038RATE METH. x 1000 * 3.724 1.715 1.3 .989 1.308(MOL/qCAT-MIN) *RATE SHIFT x 1000 * 1.771 .629 .739 .733 1.148(MOL/gCAT-MIN) *


H2 * .45 .3 .225 .15 .2CO * .3 .15 .15 .15 .2N2 * .25 .55 .625 .7 .6CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .414 .28 .21 .139 .187CO * .28 .139 .14 .142 .189N2 * .261 .561 .634 .708 .609CH4 * .022 .01 .008 .006 .008C02 * .011 .004 .004 .004 .007H20 * .012 .006 .003 .001 .001


145


RUN NUMBER * 73 74 75 76 77

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (9r)* .1 .1 .1 .1 .1FEED RATE (SCCM) * 388 388 389 388 389CONVERSION CO * .075 .078 .111 .085 .119YIELD OF CH4 * .048 .051 .08 .053 .084RATE METH. x 1000 * 2.075 2.667 4.872 3.197 5.707(MOL/gCAT-MIN) *RATE SHIFT x 1000 * 1.17 1.378 1.917 1.955 2.374(MOL/qCAT-MIN) *

FEED PARTIAL PRESSURES (ATM)** **************************-k*****************************

H2 * .25 .3 .525 .35 .585CO * .25 .3 .35 .35 .39N2 * .5 .4 .125 .3 .025CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .226 .27 .479 .318 .535CO * .237 .286 .329 .333 .368N2 * .512 .413 .132 .311 .027CH4 * .012 .016 .03 .019 .035C02 * .007 .008 .012 .012 .015H20 * .005 .008 .018 .007 .02


146



RUN NUMBER * 78 79 80 61 82

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (9r)* .1 .1 .1 .186 .186FEED RATE (SCCM) * 387 387 387 387 387CONVERSION CO * .09 .082 .08 .114 .087YIELD OF CH4 * .054 .053 .053 .071 .05RATE METH. x 1000 * 3.654 4.062 4.472 .33 .233(MOL/qCAT-MIN)RATE SHIFT x 1000 * 2.409 2.207 2.33 .2 .172(MOL/gCAT-MIN)


H2 * .39 .44 .49 .1 .075CO * .39 .44 .49 .05 .05N2 * .22 .12 .02 .85 .875CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 0


H2 * .356 .401 .449 .092 .07CO * .371 .424 .475 .045 .046N2 * .23 .126 .021 .856 .879CH4 * .022 .025 .027 .004 .003C02 * .014 .013 .014 .002 .002H20 * .007 .011 .013 .001 .001


147



RUN NUMBER * 83 84 85 86 91

TEMPERATURE (C) * 500 500 500 500 400CATALYST WEIGHT (9r)* .186 .186 .186 .186 .147FEED RATE (SCCM) * 387 388 387 387 400CONIVERSION CO * .067 .153 .135 .101 .129YIELD OF CH4 * .038 .109 .092 .056 .108RATE METH. x 1000 * .175 1.014 .849 .515 2.62(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .134 .409 .408 .419 .516(MOL/qCAT-MIN) *


H2 * .05 .2 .15 .1 .4CO * .05 .1 .1 .1 .2N2 * .9 .7 .75 .8 .2CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * 0 0 0 0 .2


H2 * .046 .176 .129 .089 .355Co * .047 .087 .088 .091 .182N2 * .903 .716 .764 .809 .209CH4 * .002 .011 .009 .006 .022C02 * .001 .004 .004 .005 .004H20 * 0 .007 .005 .001 .227


148

TABLE OF EXPERIMENTAL RESULTS0.5 RHODIUM CATALYST

RUN NUMBER * 92 93 94 95 96

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (qr)* .147 .147 .147 .147 .147FEED RATE (SCCM) * 400 400 400 400 400CONVERSION CO * .087 .058 .116 .076 .052YIELD OF CH4 * .069 .039 .092 .065 .03RATE METH. x 1000 * 1.677 .95 1.682 1.191 .553(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .446 .453 .427 .194 .4(MOL/gCAT-MIN)


H2 * .3 .2 .3 .225 .15CO * .2 .2 .15 .15 .15N2 * .3 .4 .4 .475 .55CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .2 .2 .15 .15 .15


H2 * .27 .183 .27 .201 .141CO * .188 .191 .136 .141 .143N2 * .309 .406 .411 .484 .555CH4 * .014 .008 .014 .01 .005C02 * .004 .004 .004 .002 .003H20 * .216 .207 .165 .161 .153


149



RUN NUMBER * 97 98 99 100 101

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (gr)* .147 .147 .147 .147 .147FEED RATE (SCCM) * 391 391 391 391 391CONVERSION CO * .135 .074 .052 .049 .051YIELD OF CH4 * .114 .057 .035 .034 .037RATE METH. x 1000 * 3.125 • 1.708 1.038 1.217 1.431(MOL/qCAT-MIN)RATE SHIFT x 1000 * .569 .497 .515 .535 .557(MOL/gCAT-MIN)


H2 * .46 .375 .25 .3 .325CO * .23 .25 .25 .3 .325N2 * .08 .125 .25 .1 .025CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .23 .25 .25 .3 .325


H2 * .407 .346 .232 .28 .301CO * .21 .238 .241 .291 .316N2 * .084 .129 .254 .102 .026CH4 * .028 .015 .009 .01 .012C02 * .005 .004 .004 .005 .005H20 * .265 .268 .259 .312 .341


150


RUN NUMBER * 102 103 104 105 106

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (9r)* .241 .241 .241 .241 .241FEED RATE (SCCM) * 391 391 391 391 391CONVERSION CO * .147 .136 .099 .188 .14YIELD OF CH4 * .096 .082 .036 .14 .095RATE METH. x 1000 * .349 .296 .131 1.012 .689(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .184 .197 .229 .349 .323(MOL/gCAT-MIN)


H2 * .1 .075 .05 .2 .15CO * .05 .05 .05 .1 .1N2 * .8 .825 .8 .6 .65CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .05 .05 .05 .1 .1


H2 * .089 .066 .048 .168 .128CO * .043 .044 .045 .084 .088N2 * .808 .832 .853 .617 .663CH4 * .005 .004 .002 .014 .01C02 * .003 .003 .003 .005 .005H20 * .053 .052 .049 .112 .107


151


RUN NUMBER * 107 108 109 110 111

TEMPERATURE (C) * 400 450 450 450 450CATALYST WEIGHT (9r)* .241 .095 .095 .095 .095FEED RATE (SCCM) * 391 391 391 391 390CONVERSION CO * .1 .138 .123 .096 .132YIELD OF CH4 * .05 .092 .069 .04 .085RATE METH. x 1000 * .359 3.375 2.518 1.463 2.349(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .367 1.702 1.993 2.059 1.29(MOL/9CAT-MIN) *


H2 * .1 .4 .3 .2 .3CO * .1 .2 .2 .2 .15N2 * .7 .2 .3 .4 .4CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .1 .2 .2 .2 .15


H2 * .091 .368 .277 .19 .276CO * .091 .179 .18 .184 .134N2 * .707 .208 .308 .406 .411CH4 * .005 .019 .014 .008 .013C02 * .005 .01 .011 .011 .007H20 * .101 .217 .209 .2 .16

CORRECTION FACTOR * .92 1 1 1 .964

152

TABLE OF EXPERIMENTAL RESULTS0.5%. RHODIUM CATALYST

RUN NUMBER * 112 113 114 115 116

TEMPERATURE (C) * 450 450 450 450 450CATALYST WEIGHT (9r)* .095 .095 .095 .095 .095FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .11 .092 .133 .114 .101YIELD OF CH4 * .059 .035 .089 .066 .043RATE METH. x 1000 * 1.617 .963 3.736 3.016 1.976(MOL/gCAT-MIN) *RATE SHIFT x 1000 * 1.419 1.557 1.881 2.205 2.649(MOL/gCAT-MIN) *


H2 * .225 .15 .46 .375 .25CO * .15 .15 .23 .25 .25N2 * .475 .55 .08 .125 .25CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .15 .15 .23 .25 .25


H2 * .21 .144 .427 .349 .237CO * .136 .138 .208 .229 .23N2 * .484 .556 .083 .129 .256CH4 * .009 .005 .021 .017 .011C02 * .008 .009 .011 .012 .015H20 * .154 .148 .25 .263 .252


153


RUN NUMBER * 117 118 119 120 121

TEMPERATURE (C) * 450 450 450 450 450CATALYST WEIGHT (gr)* .095 .095 .191 .191 .191FEED RATE (SCCM) * 390 390 390 390 390CON ERSION CO * .097 .104 .187 .156 .144YIELD OF CH4 * .043 .051 .088 .058 .035RATE METH. x 1000 * 2.354 3.063 .399 .264 .161(MOL/gCAT-MIN)RATE SHIFT x 1000 * 2.954 3.152 .452 .448 .494(MOL/9CAT-MIN)


H2 * .3 .325 .1 .075 .05CO * .3 .325 .05 .05 .05N2 * .1 .025 .8 .825 .85CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .3 .325 .05 .05 .05


H2 * .285 .302 .093 .072 .05Co * .278 .301 .041 .042 .043N2 * .103 .026 .807 .83 .853CH4 * .013 .017 .004 .003 .002C02 * .017 .018 .005 .005 .005H20 * .305 .336 .05 .048 .047

CORRECTION FACTOR * .887 .88 1 1 1

154


RUN NUMBER * 122 123 124 125 126

TEMPERATURE (C) * 450 450 450 500 500CATALYST WEIGHT (9r)* .191 .191 .191 .095 .095FEED RATE (SCCM) * 390 390 390 390 390CON',ERSION CO * .199 .174 .153 .139 .123YIELD OF CH4 * .117 .079 .045 .074 .05RATE METH. x 1000 * 1.071 .723 .408 2.681 1.806(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .74 .863 .983 2.386 2.674(MOL/gCAT-MIN) *


H2 * .2 .15 .1 .4 .3CO * .1 .1 .1 .2 .2N2 * .6 .65 .7 .2 .3CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .1 .1 .1 .2 .2


H2 * .177 .138 .098 .38 .291Co * .082 .084 .086 .177 .179N2 * .614 .66 .706 .206 .306CH4 * .012 .008 .005 .015 .01C02 * .008 .01 .011 .013 .015H20 * .106 .1 .095 .208 .199********************** *************************************

CORRECTION FACTOR * .98 .98 .93 1 .994

155


RUN NUMBER * 127 128 129 130 131

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (gr)* .095 .095 .095 .095 .095FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .11 .128 .121 .11 .15YIELD OF CH4 * .029 .063 .043 .023 .086RATE METH. x 1000 * 1.069 1.735 1.165 .629 3.608(MOL/9CAT-MIN) *RATE SHIFT x 1000 * 2.929 1.756 2.137 2.369 2.668(MOL/9CAT-MIN) *


H2 * .2 .3 .225 .15 .46CO * .2 .15 .15 .15 .23N2 * .4 .4 .475 .55 .08CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .2 .15 .15 .15 .23


H2 * .201 .287 .22 .154- .432CO * .18 .133 .134 .134 .204N2 * .405 .408 .481 .554 .083CH4 * .006 .01 .006 .003 .021C02 * .016 .01 .012 .013 .015H20 * .192 .153 .147 .141 .245


156


RUN NUMBER * 132 133 134 135 136

TEMPERATURE (C) * 500 500 500 500 500CATALYST NEIGHT (9r)* .095 .095 .095 .095 .193FEED RATE (SCCM) * 390 390 388 388 390CONVERSION CO * .129 .121 .112 .125 .175YIELD OF CH4 * .057 .035 .038 .042 .039RATE METH. x 1000 * 2.599 1.596 2.079 2.447 .176(MOL'gCAT-MIN) *RATE SHIFT x 1000 * 3.297 3.899 3.99 4.906 .611(MOL/gCAT-MIN)


H2 * .375 .25 .3 .325 .1CO * .25 .25 .3 .325 .05N2 * .125 .25 .1 .025 .8CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .25 .25 .3 .325 .05


H2 * .361 .249 .294 .32 .101CO * .224 .224 .273 .292 .041N2 * .129 .254 .102 .026 .803CH4 * .015 .009 .012 .014 .002C02 * .019 .022 .023 .028 .007H20 * .253 .242 .296 .32 .045


157


RUN NUMBER * 137 138 139 140 141

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (9r)* .193 .193 .193 .193 .193FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .162 .181 .219 .194 .188YIELD OF CH4 * .032 .017 .087 .058 .042RATE METH. x 1000 * .142 .075 .78 .524 .375(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .586 .738 1.187 1.223 1.321(MOL/gCAT-MIN) *


H2 * .075 .05 .2 .15 .1CO * .05 .05 .1 .1 .1N2 * .825 .85 .6 .65 .7CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .05 .05 .1 .1 .1


H2 * .077 .056 .191 .148 .103CO * .042 .041 .08 .082 .082N2 * .828 .851 .611 .658 .706CH4 * .002 .001 .009 .006 .004C02 * .007 .008 .013 .014 .015H20 * .045 .043 .097 .093 .09


158


RUN NUMBER * 142 143 144 145 146

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (gr)* 1.528 1.528 1.528 1.528 1.528FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .346 .308 .281 .593 .599YIELD OF CH4 * .194 .185 .176 .427 .426RATE METH. x 1000 * .441 .525 .602 .973 .728(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .348 .351 .357 .377 .295(MOL/qCAT-MIN) *


H2 * .2 .25 .3 .4 .3CO * .2 .25 .3 .2 .15N2 * .4 .25 .1 .2 .4CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .2 .25 .3 .2 .15


H2 * .124 .157 .193 .213 .154CO * .142 .191 .241 .098 .069N2 * .434 .275 .112 .241 .459CH4 * .042 .051 .059 .103 .073C02 * .033 .034 .035 .04 .03H20 * .226 .292 .36 .304 .216

CORRECTION FACTOR * 1 .986 .971 .989 .977

159


RUN NUMBER * 147 148 149 150 151

TEMPERATURE (C) * 400 400 450 500 450CATALYST WEIGHT (gr)* 1.528 1.528 1.528 1.528 1.526FEED RATE (SCCM) * 390 390 390 390 390CON)ERSION CO * .599 .521 .629 .643 .634YIELD OF CH4 * .395 .289 .246 .191 .244RATE METH. x 1000 * .45 .329 .56 .434 .556(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .232 .264 .871 1.031 .89(MOL/qCAT-MIN) *


H2 * .2 .15 .2 .2 .2CO * .1 .1 .2 .2 .2N2 * .6 .65 .4 .4 .4CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .1 .1 .2 .2 .2


H2 * .111 .092 .143 .191 .146CO * .043 .051 .082 .077 .081N2 * .652 .69 .444 .433 .443CH4 * .043 .031 .055 .041 .054C02 * .022 .025 .085 .098 .087H20 * .129 .112 .192 .16 .189


160


RUN NUMBER * 152 153 154 155 156

TEMPERATURE (C) * 450 450 450 450 450CATALYST WEIGHT (9r)* 1.526 1.526 1.526 1.526 1.526FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .64 .653 .51 .582 .6YIELD OF CH4 * .255 .27 .145 .196 .215RATE METH. x 1000 * .727 .925 .083 .224 .367(MOL/qCAT-MIN) *RATE SHIFT x 1000 * 1.096 1.309 .208 .44 .66(MOL/gCAT-MIN)


H2 * *.25 .3 .05 .1 .15CO * .25 .3 .05 .1 .15N2 * .25 .1 .85 .7 .55CH4 0 0 0 0 0

C02 * 0 0 0 0 0H20 * .25 .3 .05 .1 .15


H2 * .178 .205 .047 .083 .119CO * .103 .124 .025 .043 .064N2 * .287 .119 .863 .729 .588CH4 * .073 .097 .007 .02 .034C02 * .11 .137 .019 .04 .062H20 * .249 .318 .04 .084 .133


161

TABLE OF EXPERIMENTAL RESULTS0.5%, RHODIUM CATALYST

RUN NUMBER * 157 158 159 160 161

TEMPERATURE (C) * 450 450 450 500 500CATALYST WEIGHT (9r)* 1.526 1.526 1.526 .761 .761FEED RATE (SCCM) * 390 390 390 389 389CONVERSION CO * .729 .697 .639 .426 .447YIELD OF CH4 * .445 .412 .345 .127 .146RATE METH. x 1000 * 1.015 .705 .393 .579 .831(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .648 .488 .336 1.367 1.717(MOL/qCAT-MIN) *


H2 * .4 .3 .2 .2 .25CO * .2 .15 .1 .2 .25N2 * .2 .4 .6 .4 .25CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .2 .15 .1 .2 .25


H2 * .231 .18 .135 .194 .233CO * .066 .052 .039 .121 .149N2 * .243 .456 .644 .421 .27CH4 * .108 .071 .037 .027 .039C02 * .069 .049 .032 .063 .081H20 * .282 .193 .113 .174 .228

CORRECTION FACTOR * .971 .97 .971 1 .997

162


RUN NUMBER * 162 163 164 165 166******-k*l***L ******************************l***********

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (qr)* .761 .761 .761 .761 .761FEED RATE (SCCM) * 389 389 390 390 390CONVERSION CO * .452 .486 .501 .489 .411YIELD OF CH4 * .158 .252 .232 .17 .08RATE METH. x 1000 * 1.078 1.148 .797 .388 .183(MOL/gCAT-MIN) *RATE SHIFT x 1000 * 2.018 1.072 .923 .731 756(MOL/qCAT-MIN) *


H2 * .3 .4 .3 .2 .1CO * .3 .2 .15 .1 .1N2 * .1 12 .4 .6 .7CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .3 .2 .15 .1 .1


H2 * .272 .329 .253 .187 .111CO * .181 .114 .08 .053 .06N2 * .11 .222 .43 .621 .711CH4 * .052 .056 .037 .018 .008C02 * .098 .052 .043 .033 .034H20 * .286 .226 .155 .088 .076


163

TABLE OF EXPERIMENTAL RESULrS0.5% RHODIUM CATALYST

RUN NUMBER * 167 167 167 167 167

TEMPERATURE (C) * 500 500 500 500 500

CATALYST WEIGHT (gr)* .761 .761 .761 .761 .761

FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .452 .452 .452 .452 .452YIELD OF CH4 * .108 .108 .108 .108 .108

RATE METH. x 1000 * .371 .371 .371 .371 .371(MOL/qCAT-MIN)RATE SHIFT x 1000 * 1.179 1.179 1.179 1.179 1.179(MOL/gCAT-MIN)


H2 * .15 .15 .15 .15 .15

CO * .15 .15 .15 .15 .15

N2 * .55 .55 .55 .55 .55CH4 * 0 0 0 0 0

C02 * 0 0 0 0 0H20 * .15 .15 .15 .15 .15


H2 * .158 .158 .158 .158 .158

CO * .085 .085 .085 .085 .085N2 * .568 .568 .568 .568 .568CH4 * .017 .017 .017 .017 .017

C02 * .053 .053 .053 ,053 .053

H20 * .119 .119 .119 .119 .119

CORRECTION F(CTOR * .88 .88 .88 .88 .88

164

APPENDIX D

EXPERIMENTAL RUN DATA 70% Ni CATALYST

165

TABLE OF EXPERIMENTAL RESULTS70% NICKEL CATALYST

RUN NUMBER * 1 2 3 4 5

TEMPERATURE (C) * 300 300 300 300 300CATALYST WEIGHT (9r)* .105 .105 .105 .105 .105FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .137 .14 .137 .118 .125YIELD OF CH4 * .057 .073 .085 .041 .06RATE METH. x 1000 * 1.881 2.42 2.835 .338 .494(OL/gCAT-MIN)RATE SHIFT x 1000 * 2.682 2.23 1.732 .641 .547(MOL/gCAT-MIN)


H2 * .2 .3 .2 .05 .075CO * .2 .2 .2 .05 .05N2 * .4 .3 .4 .85 .825CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .2 .2 .2 .05 .05


H2 * .186 .278 .165 .048 .07CO * .177 .177 .179 .044 .044N2 * .409 .309 .414 .853 .e3CH4 * .012 .015 .018 .002 .003C02 * .017 .014 .011 .004 .003H20 * .2 .207 .214 .048 .05

CORRECTION FACTOR * 1 1 1 .985 .97

166


RUN NUMBER * 6 7 8 9 10

TEMPERATURE (C) * 300 300 300 300 300CATALYST WEIGHT (qr)* .105 .105 .105 .105 .105FEED RATE (SCCM) * 390 390 390 390 390C:ONVERSION CO * .131 .127 .129 .131 .138YIELD OF CH4 * .071 .048 .062 .077 .055RATE METH. x 1000 * .588 .803 1.034 1.28 1.369(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .496 1.315 1.112 .896 2.059(MOL/qCAT-MIN) *


H2 * .1 .1 .15 .2 .15CO * .05 .1 .1 .1 .15N2 * .8 .7 .65 .6 .55CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .05 .1 .1 .1 .15


H2 * .093 .094 .14 .185 .14CO * .044 .088 .088 .088 .132N2 * .806 .707 .658 .609 .559CH4 * .004 .005 .006 .008 .008C02 * .003 .008 .007 .005 .013H20 * .051 .098 .101 .104 .148


167


RUN NUMBER * 11 12 13 14 15

TEMPERATURE (C) * 300 300 300 300 300CATALYST WEIGHT (9r)* .105 .105 .105 .105 .105FEED RATE (SCCM) * 390 390 389 389 390C Or&ERSION CO * .142 .141 .154 .149 .157YIELD OF CH4 * .072 .085 .083 .062 .092RATE METH. x 1000 * 1.79 2.124 3.431 2.561 3.497(MOL/qCAT-MIN)RATE SHIFT x 1000 * 1.757 1.391 2.967 3.614 2.488

(MOL/gCAT-MIN)


H2 * .225 .3 .375 .25 .46CO * .15 .15 .25 .25 .23N2 * .475 .4 .125 .25 .08CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .15 .15 .25 .25 .23


H2 * .208 .277 .345 .233. .43CO * .131 .132 .221 .22 .203N2 * .485 .41 .13 .258 .084CH4 * .011 .013 .022 .016 .022C02 * .011 .009 .019 .022 .016H20 * .154 .158 .264 .251 .246


168


RUN NUMBER * 16 17 18 19 20

TEMPERATURE (C) * 300 300 400 400 400CATALYST WEIGHT (9r)* .105 .105 .06 .06 .06FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .16 .145 .105 .109 .116YIELD OF CH4 * .066 .064 .037 .052 .065RATE METH. x 1000 * 3.286 3.44 2.155 3.03 3.819(MOL/qCAT-MIN) *RATE SHIFT x 1000 * 4.691 4.407 3.976 3.346 2.931(MOL/SCAT-MIN) *


H2 * .3 .325 .2 .3 .4CO * .3 .325 .2 .2 .2N2 * .1 .025 .4 .3 .2CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .3 .325 .2 .2 .2


H2 * .28 .302 .194 .286 .381CO * .262 .29 .182 .182 .182N2 * .104 .026 .406 .306 .205CH4 * .021 .022 .007 .011 .013C02 * .029 .028 .014 .012 .01H20 * .304 .333 .197 .203 .208

CORRECTION FACTOR * .988 .981 1 .995 .989

169


RUN NUMBER * 21 22 23 24 25

TEMPERATURE (C) * 400 400 400 400 400CATALYST NEIGHT (gr)* .06 .06 .06 .06 .06FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .113 .083 .08 .082 .097YIELD OF CH4 * .042 .02 .027 .037 .029RATE METH. x 1000 * 4.013 .285 .388 .534 .847(MOL/qCAT-MIN) *RATE SHIFT x 1000 * 6.708 .92 .784 .657 1.976(MOL/9CAT-MIN) *


H2 * .325 .05 .075 .1 .1CO * .325 .05 .05 .05 .1N2 * .025 .85 .825 .8 .7CH4 * 0 0 0 0 0(02 * 0 0 0 0 0H20 * .325 .05 .05 .05 .1


H2 * .315 .05 .074 .097 .099CO * .296 .046 .046 .046 .091N2 * .026 .852 .827 .803 .704CH4 * .014 .001 .001 .002 .003CO- * .024 .003 .003 .002 .007H20 * .325 .048 .049 .05 .C97


170


RUN NUMBER * 26 27 28 29 30

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (gr)* .06 .06 .06 .06 .06FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .095 .097 .103 .102 .11YIELD OF CH4 * .042 .053 .033 .045 .054RATE METH. x 1000 * 1.214 1.553 1.463 1.979 2.347(MOL/qCAT-MIN)RATE SHIFT x 1000 * 1.559 1.29 3.044 2.474 2.47(MOL/9CAT-MIN) *


H2 * .15 .2 .15 .225 .3CO * .1 .1 .15 .15 .15N2 * .65 .6 .55 .475 .4CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .1 .1 .15 .15 .15


H2 * .144 .19 .147 .216 .289CO * .091 .091 .136 .137 .136N2 * .655 .606 .556 .482 .407CH4 * .004 .005 .005 .007 .008C02 * .005 .004 .011 .009 .009H20 * .1 .102 .146 .15 .152


171


RUN NUMBER * 31 32 33 34 35

TEMPERATURE (C) * 400 400 400 400 500CATALYST WEIGHT (9r)* .06 .06 .06 .0s .057FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .12 .113 .109 .113 .097YIELD OF CH4 * .064 .052 .038 .04 .016RATE METH. x 1000 * 4.311 3.781 2.759 3.495 .978(MOL/gCAT-MIN)RATE SHIFT x 1000 * 3.713 4.489 5.204 6.376 4.974(MOL/qCAT-MIN)


H2 * .46 .375 .25 .3 .2CO * .23 .25 .25 .3 .2N2 * .08 .125 .25 .1 .4CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .23 .25 .25 .3 .2


H2 * .441 .361 .244 .293 .208CO * .209 .228 .227 .273 .182N2 * .082 .128 .255 .102 .403CH4 * .015 .013 .01 .012 .003C02 * .013 .016 .018 .022 .016H20 * .239 .254 .246 .297 .188

CORRECTION1 FACTOR * .842 .837 .831 .827 1

172


RUN NUMBER * 36 37 38 39 40

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (9r)* .057 .057 .057 .057 .037FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .095 .101 .104 .092 .094YIELD OF CH4 * .027 .04 .024 .012 .023RATE METH. x 1000 * 1.66 2.447 2.388 .53 1.051(MOL/qCAT-MIN) *RATE SHIFT x 1000 * 4.193 3.769 7.983 3.698 3.292(MOL/SCAT-MIN) *


H2 * .3 .4 .325 .15 .225CO * .2 .2 .325 .15 .15-2 * .3 .2 .025 .55 .475CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .2 .2 .325 .15 .15


H2 * .301 .395 .333 .157 .227CO * .183 .183 .296 .137 .137N2 * .303 .203 .025 .552 .478CH4 * .005 .008 .008 .002 .003C02 * .014 .012 .026 .012 .011H20 * .194 .199 .312 .14 .144**** ** *********** *********** *******************************


173


RUN NUMBER * 41 42 43 44 45

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (gr)* .057 .06 .06 .06 .06FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .1 .126 .121 .117 .12YIELD OF CH4 * .034 .047 .035 .023 .024RATE METH. x 1000 * 1.582 3.139 2.489 1.623 2.06(MOL/qCAT-MIN) *RATE SHIFT x 1000 * 3.039 5.223 6.211 6.788 8.31(MOL/9CAT-MIN) *


H2 * .3 .46 .375 .25 .3CO * .15 .23 .25 .25 .3N2 * .4 .08 .125 .25 .1CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .15 .23 .25 .25 .3


H2 * .298 .455 .377 .26 .312CO * .136 .205 .224 .223 .268N2 * .404 .082 .127 .253 .101CH4 * .005 .011 .009 .006 .007C02 * .01 .019 .022 .024 .029H20 * .147 .228 .241 .235 .282


174

TABLE OF EXPERIMENTAL RESULTS704 NICKEL CATAL(ST

RUN NUMBER * 46 47 48 49 50

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (gr)* .111 .111 .111 .111 .111FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .149 .145 .146 .156 .157YIELD OF CH4 * .012 .021 .039 .019 .032RATE METH. x 1000 * .095 .164 .306 .301 .496(MOL/gCAT-MIN) *RATE SHIFT x 1000 * 1.072 .974 .839 2.153 1.974(MOL/gCAT-MIN) ********** ****** *******-k***********************************


H2 * .05 .075 .1 .1 .15CO * .05 .05 .05 .1 .1N2 * .85 .825 .8 .7 .65CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .05 .05 .05 .1 .1


H2 * .055 .078 .1 .108 .154CO * .043 .043 .043 .085 .085N2 * .851 .827 .803 .703 .654CH4 * .001 .001 .002 .002 .003C02 * .007 .006 .005 .014 .013H20 * .044 .045 .047 .089 .091

CORRECTION FACTOR * .993 .988 .982 1 1

175


RUN NUMBER * 51 52 53 54 55

TEMPERATURE (C) * 500 350 350 350 350CATALYST WEIGHT (gr)* .111 .063 .063 .063 .063FEED RATE (3CCM) * 390 390 390 390 390CONVERSION CO * .154 .094 .101 .103 .108YIELD OF CH4 * .047 .033 .047 .056 .039RATE METH. x 1000 * .737 1.803 2.609 3.094 3.522(MOL/gCAT-MIN) *RATE SHIFT x 1000 * 1.684 3.386 2.951 2.564 6.139(MOL/gCAT-MIN)


H2 * .2 .2 .3 .4 .325CO * .1 .2 .2 .2 .325N2 * .6 .4 .3 .2 .025CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .1 .2 .2 .2 .325


H2 * .198 .195 .288 .384 .317CO * .085 .184 .183 .184 .298N2 * .606 .405 .306 .205 .026CH4 * .005 .007 .01 .011 .013C02 * .011 .012 .011 .01 .023H20 * .095 .197 .203 .207 .324

CORRECTION FACTOR * 1 1 1 1 1

176


RUN NUMBER * 56 57 58 59 60

TEMPERATURE (C) * 350 350 350 350 350CATALYST WEIGHT (9r)* .063 .063 .063 .063 .063FEED RATE (SCCM) * 390 400 390 390 390CONVERSION CO * .091 .079 .073 .094 .095YIELD OF CH4 * .025 .03 .037 .032 .043RATE METH. x 1000 * .349 .419 .513 .874 1.183(MOL/gCAT-MIN)RATE SHIFT x 1000 * .911 .665 .495 1.729 1.426(MOL/gCAT-MIN)


H2 * .05 .073 .1 .1 .15CO * .05 .049 .05 .1 .1N2 * .85 .829 .8 .7 .65CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .05 .049 .05 .1 .1


H2 * .05 .071 .097 .097 .144CO * .046 .045 .047 .091 .091N2 * .852 .832 .803 .704 .656CH4 * .001 .001 .002 .003 .004C02 * .003 .002 .002 .006 .005H20 * .048 .048 .05 .098 .1


177


RUN NUMBER * 61 62 63 64 65

TEMPERATURE (C) * 350 350 350 350 350CATALYST WEIGHT (9r)* .063 .065 .065 .065 .065FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .094 .099 .105 .109 .121YIELD OF CH4 * .055 .035 .047 .058 .067RATE METH. x 1000 * 1.503 1.385 1.881 2.326 4.106(MOLiqCAT-MIN) *RATE SHIFT x 1000 * 1.092 2.57 2.326 2.034 3.308(MOL/gCAT-MIN) *


H2 * .2 .15 .225 .3 .46CO * .1 .15 .15 .15 .23N2 * .6 .55 .475 .4 .08CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .1 .15 .15 .15 .23


H2 * .19 .146 .216 .286 .44CO * .092 .137 .136 .136 .209N2 * .607 .556 .482 .407 .083CH4 * .006 .005 .007 .009 .016C02 * .004 .01 .009 .008 .013H20 * .103 .147 .15 .154 .24


178


RUN NUMBER * 66 67 68 69 70

TEMPERATURE (C) * 350 350 350 300 350CATALYST WEIGHT (qr)* .065 .065 .065 .069 .069FEED RATE (SCCM) * 390 390 390 390 390C:ONVERSII4 CO * .124 .114 .12 .086 .125YIELD OF CH4 * .061 .043 .048 .03 .045RATE METH. x 1000 * 4.096 2.896 3.819 1.526 2.281(MOL/9CAT-MIN) *RATE SHIFT x 1000 * 4.19 4.677 5.764 2.81 4.034(MOL/9CAT-MIN) *


H2 * .375 .25 .3 .2 .2CO * .25 .25 .3 .2 .2N2 * .125 .25 .1 .4 .4CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .25 .25 .3 .2 .2


H2 * .356 .24 .287 .195 .192CO * .226 .227 .272 .185 .178N2 * .129 .256 .103 .405 .407CH4 * .016 .011 .015 .006 .009C02 * .016 .018 .022 .011 .016H20 * .258 .249 .301 .197 .197


179


RUN NUMBER * 71 72 7$ 74 75

TEMPERATURE (C) * 400 500 300 300 300CATALYST WEIGHT (9r)* .069 .069 1.234 1.234 1.234FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .125 .105 .62 .62 .636YIELD OF CH4 * .041 .016 .246 .248 .268RATE METH. x 1000 * 2.075 .806 .346 .524 .754(MOL/gCAT-MIN) *RATE SHIFT x 1000 * 4.235 4.462 .528 .786 1.037(MOL/9 CAT-MIN) *


H2 * .2 .2 .1 .15 .2CO * .2 .2 .1 .15 .2N2 * .4 .4 .7 .55 .4CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .2 .2 .1 .15 .2


H2 * .195 .209 .067 .102. .127CO * .178 .18 .04 .062 .082N2 * .407 .403 .736 .594 .448CH4 * .008 .003 .026 .04 .06C02 * .017 .018 .039 .06 .082H20 * .195 .187 .092 .142 .202****).-k********** *k***************************************


180


70% NICKEL CATALYST

RUN NUMBER * 76 77 78 79 80

TEMPERATURE (C) * 300 350 350 350 350CATALYST WEIGHT (gr)* 1.234 1.285 1.285 1.285 1.285FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .66 .625 .648 .675 .706YIELD OF CH4 * .28 .225 .24 .256 .285RATE METH. x 1000 * 1.185 .305 .487 .692 1.16(MOL/gCAT-MIN) *RATE SHIFT x 1000 * 1.608 .541 .83 1.135 1.71(MOL/gCAT-MIN) *


H2 * .3 .1 .15 .2 .3CO * .3 .1 .15 .2 .3N2 * .1 .7 .55 .4 .1CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .3 .1 .15 .2 .3


H2 * .195 .076 .111 .145 .204CO * .122 .039 .057 .072 .106N2 * .12 .733 .593 .446 .121CH4 * .101 .024 .039 .057 .103C02 * .137 .042 .066 .093 .152H20 * .325 .086 .134 .186 .313


181


RUN NUMBER * 81 82 83 84 85

TEMPERATURE (C) * 400 400 400 400 500CATALYST WEIGHT (9r)* .62 .62 .62 .62 .766FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .52 .542 .561 .593 .434YIELD OF CH4 * .17 .192 .205 .226 .078RATE METH. x 1000 * .478 .808 1.149 1.903 .178(MOL/9CAT-MIN)RATE SHIFT x 1000 * .984 1.475 2.001 3.089 .808(MOL/9CAT-MIN)


H2 * .1 .15 .2 .3 .1CO * .1 .15 .2 .3 .1N2 * .7 .55 .4 .1 .7CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .1 .15 .2 .3 .1


H2 * .087 .123 .162 .239 .114CO * .05 .073 .096 .141 .058N2 * .725 .584 .436 .116 .711CH4 * .018 .031 .045 .078 .008C02 * .036 .056 .078 .127 .036H20 * .085 .134 .185 .298 .073


182


RUN NUMBER * 86 87 88 88 88

TEMPERATURE (C) * 500 500 500 500 500CATALYST WEIGHT (9r)* .766 .766 .766 .766 .766FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .474 .501 .541 .541 .541YIELD OF CH4 * .107 .129 .174 .174 .174RATE METH. x 1000 * .366 .587 1.188 1.188 1.188(MOL/qCAT-MIN) *RATE SHIFT x 1000 * 1.25 1.69 2.497 2.497 2.497(MOL/gCAT-MIN) *

FEED PARTIAL PRESSURES (ATM)************************************************** *****H2 * .15 .2 .3 .3 .3CO * .15 .2 .3 .3 .3

N2 * .55 .4 .1 .1 .1CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .15 .2 .3 .3 .3


H2 * .162 .208 .283 .283 .283CO * .082 .105 .154 .154 .154N2 * .568 .422 .112 .112 .112CH4 * .017 .027 .058 .058 .058C02 * .057 .078 .123 .123 .123H20 * .115 .16 .271 .271 .271******** ***-k******-****************************************


183

APPENDIX E

COMPUTER PROGRAMS

APPENDIX E. I

PROCESS CONTROL PROGRAM

10 REM THIS PROGRAM IS DESIGNED TO CONTROL THE SAMPLING OF THE FEED20 REM AND PRODUCT STREAMS. IT ALSO RECORDS THE TEMPERATURES OF THE30 REM CATALYST BED AND THE REACTANT GAS IN THE CSTR.40 REM50 REM

60 REl65 OPENW :7 "$QTO:I"66 RESERVE :770 DIM ZJt5), T1(2)80 REM POSITION THE SAMPLE VALVE SO THAT THE PROCUCT SAvMPLE IS BEING90 REM SET-UP91 FPINT "ARE SAMPLE UALVES IN 153 POSITIOt"92 PRINT * (1) YES (2) NO93 INPUT P'94 IF P'=l THEN GOTO 140

100 REM REM110 DOT(5,8,15)=153120 WAIT 3130 DOT(R5,8.15)=O140 REM142 TASK. 1,420144 T4SK 2,590150 REM160 REM INPUT THE REACTOR TEMPERATURE SETPOINT170 PRINT "INPUT THE REHCTOR SETPOINT"180 INPUT T190 REM

200 FOR. 1,=1 TO 5210 READ ZlI')220 NE 'T I230 REM231 GC,T0 330240 REM CHECK TO SEE IF THE REACTOR IS AT THE SET POINT250 REM260 V=AIN( 0,6,8)*(I.E0)270 0=2.513E 02"U-6.08BE-DS*V^2 5,536E-3*V^ 3+9. 937E-18*V^4280 S:5290 IF ABS(Q-T)(S THEN GOTO 330300 PRINT "WAITING 15 MIN. FOR REACTOR TO REACH SET POINT'310 WAIT 900320 GOTO 260330 REM NOA OPEN THE C0,H2,A4D THE FEED SAMPLE VALVES340 REM350 DOT(5.2,7j=37360 REM370 REM380 PRINT381 GOTO 590390 PRINT "THE H2,C0, AN4D FEED SAMPLE VALVES ARE OPEN"391 WAIT 600400 GOTO 590410 REM4 2', REM *-k-t&+*-A Si

430 PEi TASK 1440 REM ************************************************-*450 REM460 REM DETERMINE IF THE GC IS READY TO SAMPLE. THIS TASK IS ACTIVATED470 REM E? TASK 2.480 REM490 REM THIS TASK WILL PUT ITS SELF ON HOLD INTIL THE GC IS READY500 REll510 PEM

186

520 ACT!WATE 1 ON EVENT (7,2,0)

530 ACTIVATE 2540 REM

550 REM DISMISS UNTIL ACTIVATED BY TASK 2

56C ' lSI SS570 GOT0 520

58:C REM

600 REM TASK 2

610 REM ***************************

620 REM

630 REM THIS TASK. INJECTS THE FEED A4D PRODUCT SAMPLES.

640 REM

650 REM OPEN CHANNEL TO THE PRINTER

670 REM680 REM CHECK TO SEE IF THE REACTOR IS STILL AT THE SET POINT

690 REM691 GOTC' 880700 V=AIN(0,6,8)*( .E0)

800 O=2.513E-02*V-6.088E-0Et*V2+5.536E-13*V^3+9.937E-18*V^4810 5=5820 IF ABS(T-Q)<S THEN OT0 880

830 PRINT :7840 PRINT :7 'WITING 5 MIN. FOR REACTOR TO REACH SET POINT*

850 PRINT :7860 WAIT 3008"0 GOTO 700E:8 REm

890 REM RETURN REACTOR TEMPERATLIRE.

900 REM910 FOP J3'l TO 2

920 v=AIN 0 .J'*6.8)*( .E06)9l30 T 1 f J " 2. 513 E-0C,2*V -6. C08 E -0C8 *V'2+ 5. 5 36E -13*V 3+ 9. 9 37E -18*V ^4

940 tjET J

950 PRINT :7960 PRINT :7 "TEMPEVATURE OF :: BED= ";T1(1);" GAS, ";T1(2)

970 PRINT :7 "PRODLICT SMIPLE INJECTED AT: ";PTIME :7

971 PRINT :7 "WP"

950 PRINT :-

990 PPI T :71000 PRINT :71010 REM

1020 REM1030 [,OT, 5l=',l5=:EE

1040 WAIT 3

105) C,0Tt5.8,15)=01060 REM1070 REM ACTIU-TE TASK 1 AND DISMISS LNTIL

1080 REM THIS TASK IS RECTIVATED B TASK 1.

1090 REM1091 OT0 11201i1-1CO MCTIVATE 1

1i10 DISMISS1120 REM

1121 PRINT ",***************** PRODUCT INJECTED *******************1122 WAIT 1800112?- PRINT

1124 PRINT110 EM I'''ECT rEEE' SAMPLE

114? f'EI1150 REM CHECK TO SEE THAT THE REACTOR IS AT THE SET POINT

1160 PEtl

1161 G-,T0 12601170 ''=4TH 0.E.E'

' l£06'

1180 0=2.51.3E-02*)J-6.08S;E-08*Ut2+5,536E13

= V 3+9.937E

-18 '*V^4

1190 S=5

187

1200 IF AE:(T-Q0<S THEN GOTO 12601210 PFINT :7:13- =!',T :7 "WAITN.C 5 MIN. FOR REACTOR TO REACH SET POINT"

1240 PRINT :71250 WAIT 3001255 GOTO 1170I-: FEM1270 REM RETURN REACTOR TEMPERATURES1280 REM1u'- FC,; I =1 TO 21300 I=AIN(0,J'*G,B)*(1.EO )12'10c Tl J" ):2.SJ;3E-O2'*U-6.088~E-08*U^2+5.536i-13*U^3- +9.937E-18*V"4

1320 NEXT JI . F FINT :7 "TEMPERATURE OF :: BED= ;T (1 );" GAS= :T1(2)1331 PRINT :7 "FEED SAMPLE INJECTED AT: ";PTIME :71332 PRINT :7 "PF"1340 PRINT :71350 PRCINT :71360 REII1 ,70 REM138C' CT 5 .8,15 1521330 WAIT 31400 DCTt5.,15=01410 REM1420 REM143,C REM AT THIS POINT THE PROGRArI MAY BE STOPPED.1440 R EM1450 F'F JT :7 "**-*******************************************"1460 PRINT :71470 PEMl1480 PRE ACTIY,- T E TAsE 1 ANt DISMISS LS4TIL THIS TASK IS ACTIVATED1471, , REM0 AGAIN E' TAS 1. WHEti ACTIMATED, THE PROGRAM WILL RETURN1500 PEM TO THE T0P OF TASK 2 AND CCV1TINUE EXECUTION UNTIL STOPPED.1510 R:EM

1511 G070 15311 .--'0 4C-T1\:4TEIs CZ: i

1531 PINT ******** ************ FEED INJECTED ********************"1532 WA!T 180015??-- PP I NT153z4 Pc1540 GOCTO 5901550 ENO156 DA.,T A 0. ,2.5132785E-02,-6.0883423E-0ES,5.5358209E-131570 D -1TA 9.3720918E-18

188

APPENDIX E.2

DATA STORAGE AND ANALYSIS PROGRAM

189

REM THIS PROGRAM CONVERTS THE RAW DATA FROM THE CSTR EXPERIMENTSREM TO A USEFUL FORtfi THEN STORES IT IN A RANDOM ACCESS FILE CALLEDREM 'REDAT". ANOTHER PROGRAM CALLED PRINDAT' WILL ACCESSTHIS FILEREM AND PRINT OUT THE INFORMATION ON A PARTICULAR EXPERIMENTAL RUN.REM THE DATA IS STORED ACCORDING TO RUN NUMBER (WHICH IS ALSO THEREM FILE NUMBER).REMREM THE DATA IS INPUT THROUTH THE KEY BOARD AND IS STORED ON DISKREM IN "REDAT"REMFILENAMER$=*REDAT"OPEN FILENAMER$ AS #1 LEN,216NUL=LOF(1),216PRINT 'THE LAST RUN NUMBER WAS ";NUMCLOSE #1REMREM10 REMREMINPUT "RUN NUMBER- ";RINPUT -FLOW H2 (SCCM)- ";FHINPUT -FLOW CO (SCCM)- ";FCOINPUT -FLOW N2 (SCCM)- ";F2NINPUT 'FLOW CH4 (SCCM)= ";FCH4INPUT -FLOW C02 (SCCM)= ';FCO2INPUT "FLOW FEED SAMPLE (SCCM)= *;FSINPUT "FLOW H20 (SCCMt= ';FWPRINT ..............................INPUT 'TEMPERATURE OF REACTOR (CELCIUS). ";TRINPUT "CONVERSION OF CO. ";XINPUT "YEILD OF CH4= ";YINPUT "WEIGHT OF CATALYST USED (GRAMS). ":CATWINPUT "CONVERSION OF CO and YIELD CH4 AT STANDARD CONDITIONS: START';SC.SDINPUT "CONVERSION OF CO and YIELD CH4 AT STANDARD CONDITIONS FINISH';FCFDINPUT -TIME OF SET (START. FINISH,':SSETFSETINPUT "TIME OF FlUJ'\START. FiNISH)',SRUN.FRUNREMREMREM WAT=FW*1239.623WAT=FWTFL-WAT+FH+FCO+F2N+FCH4+FC02PH2=FH./TFLPCO=FCOTFLPN2=F2N,'TFLPCH4-FCH4.,'TFLPCO2=FCOZTFLPH20-WAT/TFLREMREMREM C ',LCULATE THE OUTLET PARTIAL PRESSURES USING CO AS A BASIS TAKEREM THE FLOW OF CO AS 1REMIH2=FH'FCOICH4=FCH4.'FCOIC02=FCO2FCOIN2=F2N.:FCOIH20.WAT'FCOSF=FS FCOREM

190

REM TOTAL PF4ODUCT FLOW INTO THE REACTOR IS THE SUMJ OF THEREM FRACTIONAL FLOWS MINUS TWCE THE VEILD OF CH4REM7 P F= 1 , IH2+ IC H4+ICO2+IN2+IH20-2'YREMREM OUTLET PARTIAL PRESSURESREMPOH2-(IH2-3*Y+(X-Y))/TPFPOCO.(1 -X)1'TPFPON2-IN2,7PFPOCH4-(ICH4+Y),'TPFPOC02-(1C02.X-Y)ITPFPOH2O.(1H20+V-(X-Y))tTPFREMREMREM CALCULATE THE RATE OF METHANATIONREMFRAC-T.(1-FST'FL)RM.(Y (FCO-FRACT)122414)/CATWREMREM RATE OF SHIFTREMRS.((X-Y'( FCO-FRACT)/2241 4)/CATW

YlELD=VTF7FL*FRACTTEM=TRREMREM THIS PART OF THE PROGRAM INSERTS THE USEFUL DATA INTOTHEREM RANDOM ACCESS FILE'REDAT'REMFILETYPES-DArREMOPEN FILENAMERS AS #1 LEN-216REMFIELD #1.8 AS H2$,8 AS CO$.8 AS N$,8 AS 04$,8 AS C2$,8 AS HO$S AS ZHS,8 AS ZCOS,8 AS ZNS.8AS ZC4$.8 AS ZC2$.8 AS ZHO$,8 AS WCOS 8 AS WC-4$S AS T$,8 AS WCW$.8 AS A$,8 AS 85.8 AS C

$,8 AS 0$,8 AS E$.8 AS FS,8 AS G$.8 AS H$,8 AS 1$.8 AS J$,8 AS K$REMREMLSET H2$=MKDS(PH2)LSET CO$-MKDS(PCO)LSET NS=MKDS(PN2)LSET C4S=MKDS(PCH4)LSET C2S=MKDS(PCO2)LSET HOS=MKDS(PH2O)LSET ZH-S=MKOS(POH2)LSET ZCO$=MKDS(POCO)LSET ZNS=MKDS(PON2)LSET ZC4S=MKDS(POCH4)LSET ZCZS=MKDS(POCQ2)LSET ZHO$=MKDS(POH2O)LSET WCO$=MKDS(CONCO)LSET WC4S=MKDS(YIELD)LSET TS=MKDS(TEM)LSET WCWS=MKDS(CATW)LSET AS=MKDS(RM)LSET BS=.MKDS(RS)ISET CS=MKDSTF)LSET DS-MKDS(SC)LSET ES=MKDS(FC)LSET FS=MKDS(SSET)LSET GS=MKDS(FSET)LSET HS=MKDS(SRUN)LSET 1S-MKD5(FRUN)LSET JS.MKDS(SD)LSET KS=MKDS'FO)

191

REMPUT #1,RREMREMCLOSE #1REMREM QUESTION IS THERE MORE DATA TO BE ENTERED?REMPRINT "DO YOU WISH TO ENTER MORE DATA ' (YES/NO)INPUT Q$IF O$=YES" THEN GOTO 10999 STOPEND

192

APPENDIX E. 3

DATA RETRIEVAL AN) PRINTING PROGRAM

193

REM PROGRAM TO PRINT DATA INTO TABLESREMDIM A(28,6)DIM N$(28)DIM M$(6)DIM P(6.6)DIM OP(6,6)SOTO 200111 PRINT *ONE RUN NUMBER IS TOO HIGH. THE LAST RUN WAS ';NUMPRINT200 PRINT"WHAT RUN NUMBERS DO YOU WANT DATA FOR?PRINT"PUT THE SIX RUN NUMBERS IN THE FORM: A.B,C.O.EFINPUT A(1 .1),A(1 .2),A(1 ,3),A(1 ,4).A(1 ,5).A(1 .6)REMFILEMAMER$-REDAT-OPEN FILEMAMERS AS #1 LEN=216NUM=LOF(1 )121 6FOR 1=1 TO 6IF NUM< A(l,l) THEN 111NEXT IREMFIELD #1,8 AS H2$.8 AS CO$,8 AS N$.8 AS C4$,8 AS C2S,8 AS HO$.8 AS ZH$,8 AS ZCO$,8 AS ZN$S8AS ZC4$.B AS ZC2S.B AS ZHOS.8 AS WCO$,8 AS WC4S.8 AS T$,8 AS WCW$,8 AS AS,8 AS B$,8 AS C

$.S AS D$,8 AS ES,8 AS F$.8 AS G$,8 AS H$,8 AS 1$.8 AS JS,8 AS K$REMFOR J=1 TO 6GET #1 ,A(1,4)A(2.J)=CVD(TS)A(3,J)=CVD(WCWS)A(4,J).CVD(C$)A(5,J).CVD(WCO$)A(6,J).CVD(WC4$)A(7.J ) =CVD (AS)A(8,J)=CVD(B$)A(9,J)=CVD(H2$)A(1 0,J)=CVD(COS)A(1 1 J)=CVD(N$)A(1 2.J)=CVD(C4$)A(1 3,J)-CVD(C2$)A(1 4 J)=CVD(HO$)A(1 5.J)=CVD(ZHS)A(16.J)=CVD(ZCOS)A)1 7,J)=CVD(ZNS)A(18,J)=CVD(ZC4$)A(1 9.J).CVD(ZC2S)A(20.J)=CVD(ZHO$)A.21,J)=CVD(D$)Ai22,J)=CVD(J$)A(23,J)-CVD(ES)A(24 .J)-CVD(KS)A(25 .J ) -CV D (FSA(26,J).CVD(GS)A(27,J)=CVD(H$)A(28 J)-CVD(IS)NEXT JCLOSE #1

194

REMREM ROUND NUMBERS TO 2 DECIMAL PLACES EXCEPT CATALYST WEIGHTREM CONVERSIO~N, YIELD. AND RATES OF SHIFT AND METHANATION WHICH WILLREM BE ROUNDED TO 3.REMFOR K-I TO 6FOR L-3 TO 6

NEXT)(IT~ L -*(,).S)lDNEXT K

REMFOR E-1 TO 6FOR F-7 TO 8A(F ,E)=(INT(l 0A6*A(FE)+.5))/l 0A 6A( F, E)-A(F E )-1000NEXT FNEXT EREMFOR F-I TO 6FOR G-7 TO 8A(G .F)=(INT( 1O '3*A(GF)+.5))II0 A3

NEXT GNEXT FFOR W-1 TO 6A(4,W)-INT(A(4.W)+.5)NEXT WREMFOR M-1 TO 6FOR N-9 TO 24A(N.M).(INT(l 0A3*A(N.M)+ .5))II OA 3NEXT NNEXT MREMFOR P-1 TO 6FOR 0=25 TO 28A(0.P)=INT(A(O,P))NEXT 0NEXT PREMREM ASSIGN STRING NAMES To VARIABLESREMN$(I)="RUN NUMBER-NS(2).-TEMPERATURE (C)-N$(3).-ATALYST WEIGHT (gr)"NS(4)--FEED RATE (SCCM)-N$(5)=CON VERSION CO"N$(6)=-YIELD OF CH4-NS'7)-"RATE METH. x 1000 (MOLE/gCAT-MIN)*NS(e;,*RATE SHIFT x 1000 (MOLE/gCAT-MIN)"N$(9).-H2-N$(10)="CO"N$(l1).-N2-N$(12)=-CH4-NS(13)--C02N$(14).-H20-NS(15)="H2'N$(16)-00-NSV17)=-N2-N 18)='CH-4"N$(19)--C02-N$(20).-H20-N$(21) .CONVERSION CO START (STD COND.)-NS(22).-YIELD CH4 START (STD COND.)-N$(23).-CONVERSION CO FINISH (STD COND.)-N$(24)--YIELD CH4 FINISH (STD COND.)-

195

NS(25)--TIME START SET-NS(26)--iME FINISH SET-N$(27)='TIME START RUN*NS(28)=-TIME FINISH RUN-REMREMREM PRINT DATA INTO TABLE FORMREMLPRINT LPRINT LPRINTLPRINT TAB(32) ,TABLE OF RESUILTS*LPRINT:LPRINT:LPRINTLPRINT STRINGS(8,')LPRINT 'RUN NUMBEFI:TAB(34). **.TAB(36); A(1 1);,TAB(44); A(1 ,2).TAB(52). A(1,3).TAB(60):A(l,4),TAB(68); A(1,5);TAB(76); A(1.6)LPRINT STRING$(80,--)FOR 0-2 TO 8LPRINT N$(0) TAB (34); -;TAB (36) ;A(O,1 );TA8(44): A(0.2) :TAB(52) ;A(0,3) .TAB(60) :A(O,4) :TAB(68); A(0.5);TAB(76). A(0,6)NEXT 0LPRINT STRINGS(80.-')LPRINTTAB(26):"FEED PARTIAL PRESSURES (ATM)*LPRINT STRINGS(80.--)FOR P-9 TO 14LPRINT NS(P);TAB(34); -;TAB(36); A(P,l):TAB(44); A(P.2);TAB(52); A(P,3):TAB(60): A(P.4);TAB(68); A(P,5);TAB(76); A(P,6)NEXT PLPRINT STRINGS(80.-)LPRtNT TAB(25);-PRODUCT PARTIAL PRESSURES (ATM)-LPRINT STRINGS(80,-)FOR V-15 TO 20IPRINT N$(V) -TAB(34); -:TAD(36): A(V. ):TAB(44): A(V.2);TAB(52); A(V,3),TAB(60); A(V,4);TAB(68), A(V.5).TAB(76): A(V,6)NEXT VLPRINT STRING$(80.--)LPRINT TAB(33);"ACTIVITY DATA*LPRINT STRINGS(80,--)FOR W-21 TO 28LPRINT N$(W):TA(34):- TAB (36)A(W, 1):TAB (44):A(W.2);TAB (52);A(W.3):TAD(60):A(W.4);TAB(6B) ,A(W.5) .TAB(76) A(W,6)NEXT WFOR WER-1 TO 20LPRINTNEXT WERSTOPEND

196

APPENDIX F

LIlzETIE STUDY DATA

197

APPENDIX F. 1

0.5% Rh 4000C

198


RUN NUMBER * 168 169 170 171 172

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (9r)* 1.524 1.524 1.524 1.524 1.524FEED RATE (SCCM) * 390 390 390 390 390COtVERSION CO * .318 .307 .298 .289 .287YIELD OF CH4 * .185 .189 .179 .179 .177RATE METH. x 1000 * .634 .647 .613 .614 .607(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .455 .404 .406 .377 .377(MOL/qCAT-MIN) *


H2 * .3 .3 .3 .3 .3CO * .3 .3 .3 .3 .3N2 * .1 .1 .1 .1 .1CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .3 .3 .3 .3 .3


H2 * .195 .187 .196 .192 .194CO * .23 .235 .236 .239 .239N2 * .113 .113 .112 .112 .112CH4 * .063 .064 .06 .06 .06C02 * .045 .04 .04 .037 .037H20 * .355 .362 .356 .359 .358

TIME OF SAMPLE (hr) * 1 11 23 34 46

199


RUN NUMBER * 173 174 175 176 177

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (qr)* 1.524 1.524 1.524 1.524 1.524FEED RATE (SCCM) * 390 390 390 390 390CONVEPSION CO * .277 .275 .278 .274 .272YIELD OF CH4 * .173 .172 .178 .173 .173RATE METH. x 1000 * .592 .59 .609 .591 .594(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .356 .351 .344 .348 .338(MOL/gCAT-MIN) *


H2 * .3 .3 .3 .3 .3CO * .3 .3 .3 .3 .3N2 * .1 .1 .1 .1 .1CH4 * 0 0 0 0 0C02 * 0 0 0 0 0H20 * .3 .3 .3 .3 .3


H2 * .196 .196 .191 .195 .194CO * .242 .243 .242 .243 .244N2 * .112 .112 .112 .112 .112CH4 * .058 .058 .06 .058 .058C02 * .035 .034 .034 .034 .033H20 * .358 .358 .362 .358 .36

TIME OF SAMPLE (hr) * 57 67 80 90 97

200

APPENDIX F.2

70% Ni 300*C

201

TABLE OF EXPERIMENTAL RESLILTS70% NICKEL CATALYST

RUN NUMBER * 89 90 91 92 93

TEMPEPATURE (C) * 300 300 300 300 300CATALYST WEIGHT (qr)* 6.043 6.043 6.043 6.043 6.043FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .888 .88 .89 .881 .877YIELD OF CH4 * .47 .465 .475 .465 .468RATE METH. x 1000 * .257 .255 .26 .254 .256(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .229 .227 .227 .228 .224(MOL/qCAT-MIN) *


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .117 .12 .114 .121 .117CO * .026 .028 .026 .028 .028N2 * .061 .061 .061 .061 .061CH4 * .224 .223 .226 .223 .224C02 * .328 .326 .328 .327 .326H20 * .243 .243 .246 .242 .245

TIME OF SAMPLE (hr) * 2 14 20 40 56

202


RUN NUMBER * 94 95 96 97 98

TEMPERATURE (C) * 300 300 300 300 300CATALYST WEIGHT (gr)* 6.043 6.043 6.043 6.043 6.043FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .874 .851 .872 .868 .872YIELD OF CH4 * .485 .474 .479 .498 .51RATE METH. x 1000 * .265 .259 .262 .273 .279(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .213 .206 .215 .202 .198(MOL/9CAT-MIN) ************ -- **-*k**********-*******************************


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .101 .105 .106 .088 .078CO * .029 .035 .03 .031 .03N2 * .061 .061 .061 .062 .062CH4 * .229 .226 .227 .234 .238C02 * .324 .319 .324 .321 .321H20 * .255 .254 .252 .265 .27

TIME OF SAMPLE (hr) * 76 96 118 136 156

203


RUN NUMBER * 99 100 101 102 103

TEMPERATURE (C) * 300 300 300 300 300CATALYST WEIGHT (9r)* 6.043 6.043 6.043 6.043 6.043FEED RATE (SCCM) * 390 390 390 390 390COVERSION CO * .859 .861 .862 .852 .863YIELD OF CH4 * .506 .506 .51 .504 .52RATE METH. x 1000 * .277 .277 .279 .276 .284(MOL/9CAT-MIN) *RATE SHIFT x 1000 * .193 .195 .192 .191 .188(MOL/gCAT-MIN)


H2 * .285 .285 .285 .285 .285Co * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .078 .08 .076 .079 .067CO * .033 .033 .033 .035 .032N2 * .062 .062 .062 .062 .062CH4 * .237 .236 .238 .236. .241C02 * .318 .319 .319 .317 .318H20 * .271 .27 .273 .271 .279

TIME OF SAMPLE (hr) * 176 196 216 250 263

204


RUN NUMBER * 104 105 106 119 120

TEMPERATURE (C) * 300 300 300 300 300CATALYST WEIGHT (gr)* 6.043 6.043 6.043 6.043 6.043FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .856 .867 .868 .867 .869YIELD OF CH4 * .509 .503 .502 .462 .503RATE METH. x 1000 * .278 .275 .275 .253 .275(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .19 .199 .2 .222 .2(MOL/gCAT-MIN) *


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .076 .083 .085 .12 .084CO * .034 .031 .031 .031 .031N2 * .062 .062 .062 .061 .062CH4 * .238 .236 .235 .222 .236C02 * .317 .32 .321 .324 .321H20 * .274 .268 .267 .244 .267

TIME OF SAMPLE (hr) * 271 307 318 30 300

205

APPENDIX F.3

70% Ni 350 0C

206


RUN NUMBER * 118 135 136 137 138

TEMPERATURE (C) * 350 350 350 350 350CATALYST WEIGHT (gr)* 4.461 4.461 4.461 4.461 4.461FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .858 .859 .857 .849 .859YIELD OF CH4 * .459 .469 .455 .443 .46RATE METH. x 1000 * .34 .347 .337 .329 .341(MOL/qCAT-MIN) *RATE SHIFT x 1000 * .295 .289 .298 .3 .295(MOL/gCAT-MIN) *


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .12 .112 .123 .131 .119CO * .033 .033 .033 .035 .033N2 * .061 .061 .06 .06 .061CH4 * .221 .224 .219 .216 .221C02 * .322 .321 .322 .321 .322H20 * .244 .249 .242 .237 .244

TIME OF SAMPLE (hr) * 234 4 50 60 80

207


RUN NUMBER * 113 114 115 116 117

TEMPERATURE (C) * 350 350 350 350 350CATALYST WEIGHT (9r)* 4.461 4.461 4.461 4.461 4.461FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .86 .858 .86 .858 .855YIELD OF CH4 * .457 .466 .456 .451 .451RATE METH. x 1000 * .339 .345 .338 .334 .334(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .299 .291 .3 .301 .299(MOL/gCAT-MIN) *


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .122 .114 .123 .127 .126CO * .032 .033 .032 .033 .033N2 * .061 .061 .06 .06 .06CH4 * .22 .223 .22 .218 .218C02 * .323 .321 .323 .323 .322H20 * .242 .248 .242 .24 .24

TIME OF SAMPLE (hr) * 16 20 35 73 102

208

TAE:LE OF EXPERIMENTAL RESULTS70Y NICKEL CATALYST

RUN NUMBER * 139 140 141 142 143

TEMPERATURE (C) * 350 350 350 350 350CATALYST WEIGHT (gr)* 4.461 4.461 4.461 4.461 4.461FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .858 .855 .858 .85 .857YIELD OF CH4 * .453 .467 .45 .459 .458RATE METH. x 1000 * .336 .346 .333 .34 .339(MOL/9CAT-MIN) *RATE SHIFT x 1000 * .3 .288 .302 .29 .296(MOL/gCAT-MIN) *


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .125 .113 .128 .118 .121CO * .033 .033 .033 .034 .033N2 * .06 .061 .06 .061 .061CH4 * .219 .223 .218 .221 .22C02 * .322 .321 .323 .32 .322H20 * .241 .249 .239 .246 .244

TIME OF SAMPLE (hr) * 120 140 160 180 200

209


RUN NUMBER * 144 145 146 147 148

TEMPERATURE (C) * 350 350 350 350 350CATALYST WEIGHT (gr)* 4.461 4.461 4.461 4.461 4.461FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .857 .858 .858 .853 .852YIELD OF CH4 * .452 .457 .45 .457 .466RATE METH. x 1000 * .335 .339 .334 .338 .346(MOL/9CAT-MIN) *RATE SHIFT x 1000 * .3 .297 .302 .294 .286(MOL/gCAT-MIN) *


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19

PRODUCT PARTIAL PRESSURES (ATM).

H2 * .126 .122 .128 .121 .112CO * .033 .033 .033 .034 .034N2 * .06 .061 .06 .06 .061CH4 * .218 .22 .218 .22 .223C02 * .322 .322 .323 .321 .32H20 * .24 .243 .239 .244 .25

TIME OF SAMPLE (hr) * 220 244 266 280 300

210

APPENDIX F.4

70% Ni 400*C

211


RUN NUMBER * 107 108 109 110 111

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (9r)* 5.302 5.302 5.302 5.302 5.302FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .817 .813 .81 .792 .81YIELD OF CH4 * .407 .409 .415 .404 .411RATE METH. x 1000 * .254 .255 .259 .252 .256(MOL/gCAT-MIN)RATE SHIFT x 1000 * .255 .252 .246 .242 .249(MOL/9CAT-MIN) *


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .155 .152 .147 .152 .15CO * .041 .042 .043 .047 .043N2 * .059 .059 .059 .059 .059CH4 * .204 .204 .206 .203 .205C02 * .317 .316 .315 .312 .315H20 * .224 .226 .23 .228 .228

TIME OF SAMPLE (hr) * 12 74 150 200 250

212


RUN NUMBER * 112 121 122 123 124

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (9r)* 5.302 5.302 5.302 5.302 5.302FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .809 .815 .816 .821 .81YIELD OF CH4 * .411 .413 .409 .394 .411RATE METH. x 1000 * .256 .257 .255 .246 .256(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .248 .251 .254 .266 .249(MOL/gCAT-MIN) *


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .15 .15 .153 .166 .15CO * .043 .042 .041 .04 .043N2 * .059 .059 .059 .059 .059CH4 * .205 .206 .204 .2 .205C02 * .315 .316 .317 .319 .315H20 * .228 .228 .225 .216 .228

TIME OF SAMPLE (hr) * 294 20 30 50 80

213


RUN NUMBER * 125 126 127 128 129

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (gr)* 5.302 5.302 5.302 5.302 5.302FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .816 .815 .81 .797 .812YIELD OF CH4 * .409 .408 .414 .403 .415RATE METH. x 1000 * .255 .254 .258 .251 .259(MOL/gCAT-MIN) *RATE SHIFT x 1000 * .254 .254 .247 .246 .248(MOL/gCAT-MIN) *


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .153 .154 .147 .154 .147CO * .041 .042 .043 .046 .042N2 * .059 .059 .059 .059 .059CH4 * .205 .204 .206 .203 .206C02 * .317 .316 .315 .313 .315H20 * .226 .225 .23 .226 .23

TIME OF SAMPLE (hr) * 101 120 135 160 180

214


RUN NUMBER * 130 131 132 133 134

TEMPERATURE (C) * 400 400 400 400 400CATALYST WEIGHT (gr)* 5.302 5.302 5.302 5.302 5.302FEED RATE (SCCM) * 390 390 390 390 390CONVERSION CO * .8 .808 .805 .793 .809YIELD OF CH4 * .402 .411 .418 .412 .408RATE METH. x 1000 * .25 .256 .26 .257 .254(MOL/qCAT-MIN)RATE SHIFT x 1000 * .248 .248 .242 .238 .25(MOL/gCAT-MIN)


H2 * .285 .285 .285 .285 .285CO * .19 .19 .19 .19 .19N2 * .05 .05 .05 .05 .05CH4 * .095 .095 .095 .095 .095C02 * .19 .19 .19 .19 .19H20 * .19 .19 .19 .19 .19


H2 * .156 .15 .143 .146 .152

CO * .045 .043 .044 .047 .043N2 * .059 .059 .059 .059 .059CH4 * .202 .205 .207 .205 .204C02 * .314 .315 .313 .311 .315H20 * .225 .228 .233 .232 .226

TIME OF SAMPLE (hr) * 220 235 260 270 280

215

SECURITY CLASSIFICATION OF THIS PAGE

Form ApprovedREPORT DOCUMENTATION PAGE oMB No 0704-0188

_ Exp Date Jun30, 1986

la REPORT SECURITY CLASSIFICATION lb RESTRICTIVE MARKINGS

UNCLASSIFIED2a SECURITY CLASSIFICAFION AUTHORITY 3. DISTRIBUTION/AVAILABILITY OF REPORT

Distribution Statement A2b DECLASSIFICATION/DOWNGRADING SCHEDULE (see 16)

4 PERFORMING ORGANIZATION REPORT NUMBER(S) S MONITORING ORGANIZATION REPORT NUMBER(S)

6a NAME OF PERFORMING ORGANIZATION 6b OFFICE SYMBOL 7a. NAME OF MONITORING ORGANIZATION

ILT Daniel Keehan (If applicable) HQDA, MILPERCEN (DAPC-OPB-D)

University of Houston IFj5. ADDRES. (ef y State, fndZIPCode). 7b ADDRESS (City, State, and ZIP Code)

ep o mi ngineering

4800 Calhoun 200 Stovall StreetHouston, TX 77004 Alexandria, VA 22332-0400

Ba. NAME OF FUNDING/SPONSORING 8b OFFICE SYMBOL 9. PROCUREMENT INSTRUMENT IDENTIFICATION NUMBERORGANIZATION (If applicable)

8c. ADDRESS (City, State, and ZIP Code) 10. SOURCE OF FUNDING NUMBERS

PROGRAM PROJECT TASK WORK UNITELEMENT NO NO NO ACCESSION NO

11 TITLE (Include Security Classification)

Carbon Monoxide Rich Methanation Kinetics on Supported Rhodium and Nickel (UNCLASSIFIED)

12 PERSONAL AUTHOR(S)

ILI Daniel Keehan

13a TYPE OF REPORT 13b TIME COVERED 14 DATE OF REPORT (Year, Month, Day) 15 PAGE COUNT

Thesis FROM860814 TO 880814 88,08,14 231

16 SUPPLEMENTARY NOTATION

(3) Distribution: Approved for public re],,ase; distribution unlimited.

17 COSATI CODES 18 SUB TERMS (Continue on reverse if necessary and identify by block number)

FIELQ GROUP SUB-GROUP Catalytic Methanationi /IfeZ-- a

Meth nation Kinetics) R~~fL. / ~

19 ABST T (Continue on reverse if necessary and identify by block number)

The utilization of carbon dioxide reforming of methane in a solar based Chemical

Energy Transmission System (CETS) relies greatly upon the development of suitable catalystsfor both the endothermic and exothermic reactions. Carbon dioxide reforming of methane

produces hydrogen and carbon monoxide at a ratio of about one, thus requirin? the

methanation reaction on the other sice of the closed loop CETS to utilixe this feed. H 2 /CO

ratios lower than three favor the formation of carbon with industrial methanation catalysts.PreliminarX tests performf p on methanation with rhodium and nickel catalysts produced two,0.5% Rh/A1 20 3 and Ni/Al20 3 , for further study.

Kinetic experiments were conducted in an isothermal continuous stirred tank reactorconstructed of a copper alloy which prevented carbon formation on reactor parts. These

experimentswere performed on pelleted 0.5% Rh/AI203 in the 400 to 500 C range and pelleted70% Ni/AI20 3 in the 300 to 500 C temperature range. In most experiments steam was added to

the reactor feed to inhibit carbon formation. Langmuir-Hinshelwood expressions were fitted 0

20 DISTRIBUTION /AVAILABILITY OF ABSTRACT 21 ABSTRACT SECURITY CLASS 'CATION

n UNCLASSIFIEDIUNLIMITED 0- SAME AS RPT El DTIC USERS UNCLASSIFIED22a NAME OF RESPONSIBLE INDIVIDUAL 22b TELEPHONE (Include Area Code) 22c OFFICE SYMBOL

ILT Daniel Keehan (713) 484-4190 (home)

DO FORM 1473, 84 MAR Bt AP tediton may be used until e'xhausted SECIRITY CLASSIFICATION OF TH'S PAGEUAll other editions are obsolete

carbon monoxide rich methanation kinetics on supported

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